Method for manufacturing a cured film, photocurable resin composition, method for manufacturing a laminate, and method for manufacturing a semiconductor device

Abstract

The present invention provides a method for manufacturing a cured film, a photocurable resin composition used in the method for manufacturing the cured film, a method for manufacturing a laminate including the method for manufacturing the cured film, and a method for manufacturing an electronic device including the method for manufacturing the cured film. The method for manufacturing the cured film includes: a first exposure step of exposing a part of a photocurable film formed from the photocurable resin composition; a development step of developing the exposed photocurable film with a developer to obtain a pattern; and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step. The photocurable resin composition has a specific composition.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a cured film, a photocurable resin composition, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device. Background Art

[0002] Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulation properties, and thus can be used for various applications. The above applications are not particularly limited, but for example, in the case of a semiconductor device for actual mounting, there are cases where a cured film containing these resins is used as an insulating film, a sealing material, a protective film, or the like. In addition, a cured film containing these resins is also used as a base film or a cover film of a flexible substrate.

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

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

[0005] Since a photocurable resin composition can be applied by a known coating method or the like, it can be said that, for example, the degree of freedom in designing the shape, size, application position, etc. of the applied photocurable resin composition is high, and the manufacturing adaptability is excellent. Considering from the viewpoint of such excellent manufacturing adaptability in addition to the high performance of polyimide, polybenzoxazole, etc., the industrial application expansion of a photocurable resin composition containing these resins is increasingly expected.

[0006] For example, Patent Document 1 describes a photosensitive resin composition characterized by containing an alkali-soluble polyimide (a), an unsaturated bond-containing compound (b), a thermally crosslinkable compound (c), and a photopolymerization initiator (d) having a specific structure.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: International Publication No. 2018 / 173840 Summary of the Invention

[0010] Technical Problem to be Solved by the Invention

[0011] Conventionally, a photocurable resin composition containing polyimide or polybenzoxazole is applied to a substrate, a pattern is formed by exposure and development, and then heated to obtain a cured film.

[0012] In the production of the above-mentioned cured film, it is desired to provide a method for producing a cured film capable of obtaining a cured film with excellent pattern shape and film strength.

[0013] An object of the present invention is to provide a method for producing a cured film capable of obtaining a cured film with excellent pattern shape and film strength, a photocurable resin composition used in the above method for producing a cured film, a method for producing a laminate including the above method for producing a cured film, and a method for producing an electronic device including the above method for producing a cured film.

[0014] Means for Solving the Technical Problem

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

[0016] <1> A method for producing a cured film, comprising:

[0017] A first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition;

[0018] A developing step of developing the exposed photocurable film with a developer to obtain a pattern; and

[0019] A second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step,

[0020] The photocurable resin composition contains:

[0021] At least one resin selected from the group including polyimide and polybenzoxazole;

[0022] A photosensitive compound A that is sensitive to the exposure wavelength in the first exposure step; and

[0023] A photosensitive compound B that is not sensitive to the exposure wavelength in the first exposure step and is sensitive to the exposure wavelength in the second exposure step,

[0024] The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step,

[0025] The above production method satisfies at least one of the following condition 1 and condition 2;

[0026] Condition 1: The resin in the photocurable resin composition contains a group that promotes a bonding reaction with other groups by the photosensitization of the photosensitive compound B in the second exposure step;

[0027] Condition 2: The above photocurable resin composition further contains a crosslinking agent having a group that promotes the bonding reaction with other groups by the photosensitivity of the photosensitive compound B in the above second exposure step.

[0028] <2> The method for producing a cured film as described in <1>, wherein

[0029] The photosensitive compound A is a compound that generates free radicals by the above first exposure step.

[0030] <3> The method for producing a cured film as described in <1> or <2>, wherein

[0031] The photosensitive compound B is a compound that generates an acid by the above second exposure step.

[0032] <4> The method for producing a cured film as described in any one of <1> or <2>, wherein

[0033] The photosensitive compound B is a compound that generates free radicals by the above second exposure step.

[0034] <5> The method for producing a cured film as described in <1> or <2>, wherein

[0035] The photosensitive compound B is a compound that generates a base by the above second exposure step.

[0036] <6> The method for producing a cured film as described in <1>, wherein

[0037] The photosensitive compound A is a photoinitiator for free radical polymerization, and the photosensitive compound B is a photoacid generator.

[0038] <7> The method for producing a cured film as described in <1>, wherein

[0039] Both the photosensitive compound A and the photosensitive compound B are photoinitiators for free radical polymerization.

[0040] <8> The method for producing a cured film as described in any one of <1> to <7>, wherein

[0041] The exposure in the above first exposure step is exposure based on i-ray.

[0042] <9> A photocurable resin composition for use in the method for producing a cured film as described in any one of <1> to <9>.

[0043] <10> A photocurable resin composition, wherein

[0044] The above photocurable resin composition contains: at least one resin selected from the group consisting of polyimide and polybenzoxazole, and photosensitive compounds A and B having a difference in maximum absorption wavelength of 80 nm or more.

[0045] The above photosensitive compound A is a compound that changes the solubility of the above photocurable film in the above developer in the following first exposure step.

[0046] The above photocurable resin composition is used in a method for manufacturing a cured film that satisfies at least one of the following conditions 1 and 2 and includes the following steps:

[0047] First exposure step: exposing a part of the photocurable film formed from the photocurable resin composition.

[0048] Development step: developing the exposed photocurable film with a developer to obtain a pattern; and

[0049] Second exposure step: exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step.

[0050] Condition 1: The above resin in the above photocurable resin composition contains a group that promotes a bonding reaction with other groups through the photosensitivity of the above photosensitive compound B in the second exposure step.

[0051] Condition 2: The above photocurable resin composition further contains a crosslinking agent having a group that promotes a bonding reaction with other groups through the photosensitivity of the above photosensitive compound B in the second exposure step.

[0052] <11>A method for manufacturing a laminate, which includes the method for manufacturing a cured film according to any one of <1> to <8>.

[0053] <12>A method for manufacturing an electronic device, which includes the method for manufacturing a cured film according to any one of <1> to <8> or the method for manufacturing a laminate according to <11>.

[0054] Advantages of the Invention

[0055] According to the present invention, there is provided a method for manufacturing a cured film capable of obtaining a cured film having excellent pattern shape and film strength, a photocurable resin composition used in the method for manufacturing a cured film, a method for manufacturing a laminate including the method for manufacturing a cured film, and a method for manufacturing an electronic device including the method for manufacturing a cured film. Detailed Embodiments

[0056] Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments.

[0057] In this specification, the numerical range indicated by the symbol "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively.

[0058] In this specification, the term "process" not only represents an independent process, but also represents a process that cannot be clearly distinguished from other processes as long as the required function of the process can be achieved.

[0059] Regarding the notation of groups (atomic groups) in this specification, the notation of unsubstituted and substituted simultaneously includes groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl without substituents (unsubstituted alkyl) but also alkyl with substituents (substituted alkyl).

[0060] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. And, as the light used for exposure, there can be mentioned the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiations.

[0061] In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either one of them, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid" or either one of them, and "(meth)acryloyl" means both "acryloyl" and "methacryloyl" or either one of them.

[0062] In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0063] In this specification, the total solid content represents the total mass of the components obtained by removing the solvent from the total components of the composition. And, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0064] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement) and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be determined, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. Also, unless otherwise specified, UV light (ultraviolet light) with a wavelength of 254 nm is used as the detector in GPC measurement.

[0065] In this specification, regarding the positional relationship of each layer constituting the laminate, when it is described as "upper" or "lower", it is sufficient that there is another layer above or below the layer that serves as a reference among the multiple layers of interest. That is, a third layer or a third element may be further sandwiched between the layer serving as a reference and the other layer, and the layer serving as a reference and the other layer do not need to be in contact. Also, unless otherwise specified, the direction of stacking layers on the substrate is called "upper", or when there is a photocurable layer, the direction from the substrate toward the photocurable layer is called "upper", and the opposite direction is called "lower". In addition, these upper and lower directions are set for convenience in this specification, and in actual practice, the "upper" direction in this specification may be different from the vertically upward direction.

[0066] In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. Also, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component.

[0067] In this specification, unless otherwise specified, the temperature is 23°C and the atmospheric pressure is 101,325 Pa (1 atmosphere).

[0068] In this specification, a combination of preferred modes is a more preferred mode.

[0069] (Method for manufacturing a cured film)

[0070] The first mode of the method for manufacturing a cured film of the present invention includes: a first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition; a development step of developing the exposed photocurable film with a developer to obtain a pattern; and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step. The photocurable resin composition includes at least one resin selected from the group including polyimide and polybenzoxazole (hereinafter, also referred to as "specific resin"), a photosensitive compound A sensitive to the exposure wavelength in the first exposure step, and a photosensitive compound B not sensitive to the exposure wavelength in the first exposure step but sensitive to the exposure wavelength in the second exposure step. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step. The manufacturing method satisfies at least one of the following condition 1 and condition 2.

[0071] Condition 1: The resin in the photocurable resin composition includes a group that promotes a bonding reaction with other groups by the photosensitization of the photosensitive compound B in the second exposure step.

[0072] Condition 2: The photocurable resin composition further includes a crosslinking agent having a group that promotes a bonding reaction with other groups by the photosensitization of the photosensitive compound B in the second exposure step.

[0073] The second mode of the method for manufacturing a cured film of the present invention includes: a first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition; a development step of developing the exposed photocurable film with a developer to obtain a pattern; and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step. The photocurable resin composition includes at least one resin selected from the group including polyimide and polybenzoxazole, and photosensitive compound A and photosensitive compound B having a difference in maximum absorption wavelength of 80 nm or more. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step. The manufacturing method satisfies at least one of the above condition 1 and condition 2.

[0074] Except that the photosensitive compound A and the photosensitive compound B are different, the first mode and the second mode are the same mode.

[0075] Hereinafter, the first mode will be simply referred to as "the first mode", the second mode will be simply referred to as "the second mode", and the first mode and the second mode will be collectively referred to as "the method for manufacturing a cured film of the present invention".

[0076] According to the method for manufacturing a cured film of the present invention, a cured film having excellent pattern shape and film strength can be obtained.

[0077] The mechanism for obtaining the above effects is not yet clear, but it can be speculated as follows.

[0078] Conventionally, a photocurable resin composition containing polyimide or polybenzoxazole has been applied to a substrate, a pattern has been formed by exposure and development, and then heated to obtain a cured film.

[0079] The inventors of the present invention have found that there is room for improvement in terms of deformation of the pattern after exposure and development due to expansion, contraction, etc. during the above heating and subsequent cooling.

[0080] As a result of intensive studies by the inventors of the present invention, it has been found that by performing exposure in two stages, i.e., the above-described first exposure step and second exposure step, on a photocurable film formed from the above-described photocurable resin composition, a cured film in which the above-described deformation is suppressed can be obtained, and thus the present invention has been completed.

[0081] According to the method for manufacturing a cured film of the present invention, since a cured film can be obtained without performing heating for curing (for example, heating at 180 °C or higher), it is considered that the process can also be shortened.

[0082] In addition, it is considered that a cured film having excellent film strength can be easily obtained because the crosslinking density in the cured film increases due to the above two-stage exposure.

[0083] In addition, it is considered that a cured film having excellent solvent resistance can be easily obtained for the same reason as the above increase in crosslinking density.

[0084] Here, in Patent Document 1, neither a method for manufacturing a cured film including a first exposure step and a second exposure step is described nor suggested.

[0085] Hereinafter, the method for manufacturing a cured film of the present invention will be described in detail.

[0086] <First Exposure Step>

[0087] The method for manufacturing a cured film of the present invention includes a first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition.

[0088] In the first exposure step, the photosensitive compound A described later is sensitized, and the solubility of the photocurable film in the developer changes.

[0089] Specifically, for example, when the photosensitive compound A is a photoinitiator described later, polymerization occurs in the photocurable film, and the solubility of the photocurable film after the first exposure step in the developer decreases.

[0090] Further, for example, when the photosensitive compound A is a photoacid generator described later and the developer is an alkaline developer described later, an acid is generated in the photocurable film, and the solubility in the developer increases.

[0091] Furthermore, for example, when the photosensitive compound A is a photoacid generator described later and the developer is an organic solvent described later, an acid is generated in the photocurable film, and the solubility in the developer decreases.

[0092] As described above, in the first exposure step, the photosensitization of the photosensitive compound A can promote the bonding reaction between the crosslinkable groups contained in the specific resin or crosslinking agent and other groups, thereby changing the solubility of the photocurable film in the developer. Alternatively, the solubility of the photocurable film in the developer can be changed by using the product generated by a chemical change (photosensitization based on the photosensitive compound A).

[0093] That is, the photocurable film in the present invention can be a positive-type photocurable film or a negative-type photocurable film.

[0094] A positive-type photocurable film refers to a photocurable film in which the exposed portion (exposed area) in the first exposure step is removed by the developer, and a negative-type photocurable film refers to a photocurable film in which the unexposed portion (unexposed area) in the first exposure step is removed by the developer.

[0095] In the first mode of the method for manufacturing a cured film of the present invention, the exposure wavelength in the first exposure step may be appropriately set to a wavelength at which the photosensitive compound A described later has sensitivity and the photosensitive compound B does not have sensitivity. Preferably, it is 190 to 1,000 nm, more preferably 240 to 550 nm, and further preferably 300 to 380 nm.

[0096] In the second mode of the method for manufacturing a cured film of the present invention, the exposure wavelength in the first exposure step may be appropriately set to the following wavelength: a wavelength near the maximum absorption wavelength of the photosensitive compound A described later (for example, a wavelength within the range of ±10 nm from the maximum absorption wavelength, etc.) and a wavelength having a sufficient distance from the maximum absorption wavelength of the photosensitive compound B (for example, a wavelength outside the range of ±20 nm from the maximum absorption wavelength, etc.). Preferably, it is 190 to 1,000 nm, more preferably 240 to 550 nm, and further preferably 300 to 380 nm.

[0097] Regarding the exposure wavelength, when described in relation to the light source, examples include (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g rays (wavelength 436 nm), h rays (wavelength 405 nm), i rays (wavelength 365 nm), wide (g, h, and i rays, three wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonic of YAG laser 532 nm, third harmonic 355 nm, etc. Regarding the photocurable resin composition of the present invention, exposure based on i rays is preferred. Thereby, high exposure sensitivity can be particularly obtained.

[0098] Furthermore, from the viewpoints of operability and productivity, a wide (g, h, and i rays, three wavelengths) light source of a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferred.

[0099] In order to suppress the photosensitivity of the photosensitive compound B, a filter for removing specific wavelengths or the like can be used in these light sources.

[0100] As a method for exposing a part of the photocurable film in the first exposure step, examples include an exposure method using a known photomask, an exposure method for exposing a part of the photocurable film by laser exposure, etc.

[0101] In the first mode of the method for manufacturing a cured film of the present invention, the exposure amount in the first exposure step, in terms of the exposure energy conversion at the wavelength at which the photosensitive compound A has sensitivity, is preferably 100 to 10,000 mJ / cm 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0102] In the second mode of the method for manufacturing a cured film of the present invention, the exposure amount in the first exposure step, in terms of the exposure energy conversion at the maximum absorption wavelength of the photosensitive compound A, is preferably 100 to 10,000 mJ / cm 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0103] <Post-exposure heating step>

[0104] The method for manufacturing a cured film of the present invention may include a step of heating the exposed photocurable film after the above first exposure step and before the developing step (post-exposure heating step).

[0105] The heating temperature in the post-exposure heating process is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[0106] The heating time in the post-exposure heating process is preferably 1 minute to 300 minutes, more preferably 5 minutes to 120 minutes.

[0107] Regarding the heating rate in the post-exposure heating process, from the temperature at the start of heating to the maximum heating temperature, it is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute.

[0108] Moreover, the heating rate can be appropriately changed during heating.

[0109] As the heating mechanism in the post-exposure heating process, there is no particular limitation, and known heating plates, ovens, infrared heaters, etc. can be used.

[0110] Also, during heating, it is preferably carried out in an atmosphere with a low oxygen concentration, such as by flowing inert gases such as nitrogen, helium, and argon, or under reduced pressure.

[0111] <Film formation process>

[0112] The method for manufacturing the cured film of the present invention may include a film formation process of forming a photocurable film from a photocurable resin composition.

[0113] The above-mentioned photocurable film in the first exposure process may be a photocurable film formed by the film formation process, or a photocurable film obtained by methods such as purchasing.

[0114] The film formation process is preferably a process of applying a photocurable resin composition on a substrate to form a film (layer) and obtaining a photocurable film.

[0115] 〔Substrate〕

[0116] The type of substrate can be appropriately set according to the use, but there is no particular limitation. Examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), etc. In the present invention, in particular, semiconductor manufacturing substrates are preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0117] Moreover, a bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like can be provided on the surface of these substrates.

[0118] Moreover, the shape of the substrate is not particularly limited and may be a circular shape or a rectangular shape.

[0119] Regarding the size of the substrate, if it is a circular shape, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as the substrate, for example, a plate-shaped substrate (substrate plate) is used.

[0120] Moreover, when forming a photocurable film on the surface of the resin layer or the metal layer, the resin layer or the metal layer serves as the substrate.

[0121] As a method for applying the photocurable resin composition to the substrate, coating is preferred.

[0122] Specifically, as the application method, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spraying method, spin coating method, slot coating method, inkjet method, etc. can be exemplified. From the viewpoint of the thickness uniformity of the photocurable film, spin coating method, slot coating method, spraying method, and inkjet method are more preferred, and from the viewpoint of easily obtaining the effects of the present invention, slot coating method is preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a photocurable film with a desired thickness can be obtained. Moreover, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating method, spraying method, inkjet method, etc. are preferred, and for a rectangular substrate, slot coating method, spraying method, inkjet method, etc. are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.

[0123] Moreover, according to the viscosity of the photosensitive resin composition or the set film thickness, it is also preferred to apply it at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Moreover, in order to obtain a uniform film thickness, it is also possible to perform coating by combining multiple rotation speeds.

[0124] Moreover, it is also possible to apply a method of transferring a coating film formed by previously applying on a pseudo support by the above-mentioned applying method to the substrate.

[0125] Regarding the transfer method, in the present invention, it is also possible to preferably use the production methods described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592.

[0126] Moreover, a step of removing excess film at the end of the substrate may also be performed. Examples of such steps include edge bead removal (EBR), backside rinse, etc.

[0127] Further, the following pre-wetting process may also be employed: before coating the resin composition on the substrate, various solvents are coated on the substrate to improve the wettability of the substrate, and then the resin composition is coated.

[0128] <Drying process>

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

[0130] The preferred drying temperature is 50 to 150 °C, more preferably 70 °C to 130 °C, and further preferably 90 °C to 110 °C. As the drying time, for example, 30 seconds to 20 minutes is exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of the solvent in the photocurable resin composition is large, vacuum drying and heat drying can also be combined. In heat drying, a hot plate, a hot air oven, etc. can be used, and there is no particular limitation.

[0131] <Developing process>

[0132] The method for manufacturing the cured film of the present invention includes a developing process of obtaining a pattern by developing the above-mentioned exposed photocurable film with a developer.

[0133] By developing, one of the exposed portion and the non-exposed portion is removed. As long as the desired pattern can be formed, the developing method is not particularly limited. For example, developing methods such as liquid covering, spraying, dipping, and ultrasonic waves can be employed.

[0134] Developing is carried out using a developer. As the developer, if it is negative development, a developer for removing the unexposed portion (non-exposed portion) can be used without particular limitation, and if it is positive development, a developer for removing the exposed portion (exposed portion) can be used without particular limitation.

[0135] In the present invention, the case where an alkali developer is used as the developer is referred to as alkali development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is referred to as solvent development.

[0136] In alkali development, as the developer, a developer in which the content of the organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably a developer containing no organic solvent, based on the total mass of the developer.

[0137] The developer in alkali development is more preferably an aqueous solution having a pH of 10 to 15.

[0138] Examples of the alkali compound contained in the developer in alkali development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia, or amines. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), or tetraethylammonium hydroxide. Among them, a metal-free alkali compound is preferred, and an ammonium compound is more preferred. TMAH is even more preferred. For example, when TMAH is used, the content of the basic compound in the developer in the total mass of the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass.

[0139] The alkali compound may be only one kind or two or more kinds. When there are two or more kinds of alkali compounds, it is preferred that their total is within the above range.

[0140] In solvent development, the developer more preferably contains 90% by mass or more of an organic solvent relative to the total mass of the developer. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula in ChemBioDraw (chemical biology drawing).

[0141] Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-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., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., cyclic terpenes such as limonene, etc., and as sulfoxides, dimethyl sulfoxide can be preferably cited.

[0142] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. And when the developer contains an organic solvent, one kind of organic solvent can be used or two or more kinds can be used in combination.

[0143] When the developer contains an organic solvent, the developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, further preferably 80% by mass or more of the organic solvent, and particularly preferably 90% by mass or more of the organic solvent. And 100% by mass of the developer can be the organic solvent.

[0144] The developer may further contain other components.

[0145] As other components, for example, known surfactants, known antifoaming agents, etc. can be cited.

[0146] 〔Supply method of developing solution〕

[0147] As long as a desired pattern can be formed, the supply method of the developing solution is not particularly limited. There are methods of immersing the substrate in the developing solution, supplying the developing solution onto the substrate with a nozzle, or continuously supplying the developing solution. The type of nozzle is not particularly limited, and examples include a direct current nozzle, a spray nozzle, a mist nozzle, etc.

[0148] From the viewpoints of the permeability of the developing solution, the removability of the non-image portion, and the manufacturing efficiency, a method of supplying the developing solution with a direct current nozzle or a method of continuously supplying with a mist nozzle is preferred. From the viewpoint of the permeability of the developing solution to the image portion, a method of supplying with a mist nozzle is more preferred.

[0149] Moreover, the following process can be adopted: after continuously supplying the developing solution with a direct current nozzle, rotate the substrate to remove the developing solution from the substrate, after spin-drying, continuously supply again with a direct current nozzle, and then rotate the substrate to remove the developing solution from the substrate, and this process can be repeated multiple times.

[0150] Moreover, as the supply method of the developing solution in the developing process, a process of continuously supplying the developing solution onto the substrate, a process of keeping the developing solution in a substantially stationary state on the substrate, a process of vibrating the developing solution on the substrate by using ultrasonic waves, etc., and a process combining these can be adopted.

[0151] As the developing time, it is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, and it is usually 10 to 45°C, preferably it can be carried out at 20 to 40°C.

[0152] In the developing process, after the treatment using the developing solution, rinsing can be further carried out. Moreover, a method such as supplying the rinsing solution before the developing solution in contact with the pattern is completely dried can also be adopted.

[0153] In the case of solvent development, it is preferably rinsed with an organic solvent different from the developing solution. For example, propylene glycol monomethyl ether acetate can be cited. The rinsing time is preferably 5 seconds to 5 minutes. Moreover, a process including both the application of the developing solution and the rinsing solution can also be included between development and rinsing. The time of the above process is preferably 1 second to 5 minutes.

[0154] In the case of alkali development, it is preferably rinsed with pure water.

[0155] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and further preferably 5 seconds to 1 minute.

[0156] The temperature of the rinsing liquid during rinsing is not particularly limited, preferably 10 to 45°C, more preferably 18 to 30°C.

[0157] As the organic solvent when the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetic acid alkyl esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkoxypropionic acid alkyl esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (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., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, preferably dimethyl sulfoxide, and as alcohols, preferably methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0158] When the rinsing liquid contains an organic solvent, one kind of organic solvent or two or more kinds thereof can be used in combination. In the present invention, in particular, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

[0159] When the rinsing liquid contains an organic solvent, the rinsing liquid is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Moreover, 100% by mass of the rinsing liquid can be an organic solvent.

[0160] The rinsing liquid may further contain other components.

[0161] Examples of other components include known surfactants and known antifoaming agents.

[0162] [Supply method of rinsing liquid]

[0163] As long as a desired pattern can be formed, the supply method of the rinsing liquid is not particularly limited, and there are methods of immersing a substrate in the rinsing liquid, liquid development on the substrate, supplying the rinsing liquid to the substrate with a spray head, and continuously supplying a developing solution to the substrate through a DC nozzle or the like.

[0164] From the viewpoints of the permeability of the rinsing liquid, the removability of the non-image portion, and the manufacturing efficiency, there are methods of supplying the rinsing liquid with a spray nozzle, a DC nozzle, a spray nozzle, etc., and the method of continuously supplying with a spray nozzle is preferred. From the viewpoint of the permeability of the rinsing liquid to the image portion, the method of supplying with a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a DC nozzle, a spray nozzle, and a spray nozzle.

[0165] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after the above exposure using a DC nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle.

[0166] Moreover, as the supply method of the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially stationary state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasonic waves, and a step of combining these can be adopted.

[0167] <Second exposure step>

[0168] The method for manufacturing a cured film of the present invention includes a second exposure step of exposing the above pattern with light including light having a wavelength different from the wavelength of the light used in the above first exposure step.

[0169] It is considered that in the second exposure step, the photosensitive compound B is photosensitized, and the film strength and solvent resistance of the cured film are improved.

[0170] For example, when the photosensitive compound B is a photoinitiator for free radical polymerization, the radical polymerizable groups contained in a crosslinking agent, a specific resin, etc. are polymerized, and the film strength and solvent resistance of the cured film are improved.

[0171] Moreover, for example, when the photosensitive compound B is a photoacid generator, the crosslinkable groups contained in a crosslinking agent, a specific resin, etc. are polymerized, and the film strength and solvent resistance of the cured film are improved.

[0172] Furthermore, for example, when the photosensitive compound B is a photo-base generator, the crosslinkable groups contained in a crosslinking agent, a specific resin, etc. are polymerized, and the film strength and solvent resistance of the cured film are improved.

[0173] In the first mode of the method for manufacturing the cured film of the present invention, the exposure light in the second exposure step only needs to include light having a wavelength to which the photosensitive compound B is sensitive, and may further include light having a wavelength to which the photosensitive compound A is sensitive.

[0174] In the second mode of the method for manufacturing the cured film of the present invention, the exposure light in the second exposure step only needs to include light having a wavelength near the maximum absorption wavelength of the photosensitive compound B (for example, a wavelength within the range of ±10 nm of the maximum absorption wavelength of the photosensitive compound B, etc.), and may further include light having a wavelength near the maximum absorption wavelength of the photosensitive compound A (for example, a wavelength within the range of ±10 nm of the maximum absorption wavelength of the photosensitive compound A, etc.).

[0175] That is, in the second exposure step, the photosensitive compound A may or may not be photosensitized.

[0176] When the photocurable film is a negative-type photocurable film, from the viewpoints of the film strength and solvent resistance of the obtained cured film, the exposure light in the second exposure step preferably further includes light having a wavelength to which the photosensitive compound A is photosensitive.

[0177] For example, when the photosensitive compound A is a photoinitiator for free radical polymerization and the photosensitive compound B is an acid generator, and in the second exposure step, in addition to the photosensitive compound B, the photosensitive compound A is also photosensitized, not only crosslinking based on acid but also free radical polymerization further proceeds, and thus it is considered that the film strength and solvent resistance of the obtained cured film are further improved.

[0178] As described above, by further including light having a wavelength to which the photosensitive compound A is photosensitive in the exposure light in the second exposure step, a cured film having excellent film strength and solvent resistance can sometimes be obtained.

[0179] In the first aspect of the method for manufacturing a cured film of the present invention, the wavelength of the light included in the exposure light in the second exposure step, which is sensitive to the photosensitive compound B, can be appropriately set in consideration of the sensitivity of the photosensitive compound B described later. It is preferably 190 to 1,000 nm, more preferably 200 to 550 nm, and still more preferably 200 to 280 nm.

[0180] In the first aspect of the method for manufacturing a cured film of the present invention, the wavelength of the light included in the exposure light in the second exposure step, which is sensitive to the photosensitive compound A, can be appropriately set in consideration of the sensitivity of the photosensitive compound A described later. It is preferably 190 to 1,000 nm, more preferably 240 to 550 nm, and still more preferably 300 to 380 nm.

[0181] In the second aspect of the method for manufacturing a cured film of the present invention, the exposure wavelength in the second exposure step is appropriately set to a wavelength near the maximum absorption wavelength of the photosensitive compound B described later (for example, a wavelength within the range of ±10 nm of the maximum absorption wavelength of the photosensitive compound B), preferably 190 to 1,000 nm, more preferably 200 to 550 nm, and still more preferably 200 to 280 nm.

[0182] In the second aspect of the method for manufacturing a cured film of the present invention, the exposure light in the second exposure step may include light having a wavelength near the maximum absorption wavelength of the photosensitive compound A described later (for example, a wavelength within the range of ±10 nm of the maximum absorption wavelength of the photosensitive compound A). As the wavelength of such light, it can be appropriately set in consideration of the maximum absorption wavelength of the photosensitive compound A, preferably 190 to 1,000 nm, more preferably 240 to 550 nm, and still more preferably 300 to 380 nm.

[0183] Regarding the exposure wavelength, when described in relation to the light source, examples include (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide (g, h, i-rays, three wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonic 532 nm and third harmonic 355 nm of YAG lasers, etc. In the method for manufacturing a cured film of the present invention, in particular, exposure based on a high-pressure mercury lamp is preferred.

[0184] In order to suppress the photosensitivity of the photosensitive compound A in the second exposure step, a filter that removes specific wavelengths or the like can be used in these light sources. However, in order to promote the photosensitivity of the photosensitive compound A in the second exposure step, it is preferably not to use a filter or the like, but to use a light source that includes various wavelengths of light in the range of 200 to 600 nm, such as the above-mentioned high-pressure mercury lamp.

[0185] In the second exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferred to expose the entire pattern.

[0186] In the first mode of the method for manufacturing a cured film of the present invention, the exposure amount in the second exposure step, in terms of the exposure energy conversion at the wavelength at which the photosensitive compound B has sensitivity, is preferably 100 to 20,000 mJ / cm 2 and more preferably 200 to 15,000 mJ / cm 2 。

[0187] In the second mode of the method for manufacturing a cured film of the present invention, the exposure amount in the second exposure step, in terms of the exposure energy conversion at the maximum absorption wavelength of the photosensitive compound B, is preferably 100 to 20,000 mJ / cm 2 and more preferably 200 to 15,000 mJ / cm 2 。

[0188] From the viewpoints of the pattern shape, film strength, and solvent resistance of the obtained cured film, the temperature of the photocurable film in the second exposure step is preferably 20 to 170 °C, more preferably 30 to 150 °C, and further preferably 50 to 130 °C.

[0189] The film thickness of the cured film obtained through the second exposure step can be set to 0.5 μm or more, and can also be set to 1 μm or more. And as the upper limit value, it can be set to 100 μm or less, and can also be set to 40 μm or less.

[0190] <Heating step>

[0191] From the viewpoints of shortening the manufacturing time and saving energy of the manufacturing method, the method for manufacturing a cured film of the present invention preferably does not include a step of heating the pattern obtained through the development step (heating step).

[0192] Specifically, from the viewpoint of improving the pattern shape, it is preferably not to include a step of heating the pattern at 200 °C or higher after the development step, and more preferably not to include a step of heating the pattern at 160 °C or higher.

[0193] When a heating step is included, the temperature from the starting temperature at the start of heating to the maximum heating temperature is preferably increased at a rate of 1 to 12 °C per minute, more preferably 2 to 10 °C per minute, and still more preferably 3 to 10 °C per minute. By setting the heating rate to 1 °C per minute or more, productivity can be ensured while preventing excessive volatilization of the acid or solvent. By setting the heating rate to 12 °C per minute or less, the residual stress of the pattern can be alleviated.

[0194] In addition, in the case of an oven capable of rapid heating, the temperature from the starting temperature at the start of heating to the maximum heating temperature is preferably increased at a rate of 1 to 8 °C per second, more preferably 2 to 7 °C per second, and still more preferably 3 to 6 °C per second.

[0195] When a heating step is included, the heating time (the heating time at the maximum heating temperature) is preferably 30 seconds to 360 minutes, more preferably 45 seconds to 300 minutes, and still more preferably 1 minute to 240 minutes.

[0196] Regarding the heating step, from the aspect of preventing decomposition of a specific resin, it is preferably carried out in an environment with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[0197] The heating mechanism in the heating step is not particularly limited, and examples thereof include a heating plate, an electric heating oven, a hot air oven, etc.

[0198] <Metal layer forming step>

[0199] The method for manufacturing the cured film of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the cured film after the second exposure step.

[0200] The metal layer is not particularly limited, and existing metal types can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. More preferably, copper and aluminum are used, and still more preferably, copper is used.

[0201] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Laid-Open No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be cited.

[0202] As the thickness of the metal layer, in the thickest part, it is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and still more preferably 1 to 10 μm.

[0203] <Usage>

[0204] As fields where the cured film obtained by the method for producing a cured film of the present invention can be applied, there can be mentioned insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. In addition, there can be mentioned sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or cases where patterns are formed by etching insulating films for actual mounting applications as described above. Regarding these applications, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide", April 2008, supervised by Masaki Kakinuma, CMC Technical Library "Fundamentals and Development of Polyimide Materials", published in November 2011, Japan Polyimide & Aromatic Polymer Research Society / edited "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc.

[0205] In addition, the cured film obtained by the method for producing a cured film of the present invention can also be used in the production of printing plates such as offset printing plates or screen printing plates, the use of molded parts in etching, the production of protective paints and dielectric layers in electronics, especially in microelectronics, etc.

[0206] (Method for manufacturing a laminate)

[0207] The method for manufacturing a laminate of the present invention preferably includes the method for manufacturing a cured film of the present invention.

[0208] The laminate obtained by the method for manufacturing a laminate of the present invention is a laminate including two or more cured films, and it can also be a laminate having 3 to 7 layers laminated.

[0209] Among the two or more cured films included in the above laminate, at least one is a cured film obtained by the method for manufacturing a cured film of the present invention. From the viewpoint of improving the pattern shape of the cured film, all the cured films included in the above laminate are preferably cured films obtained by the method for manufacturing a cured film of the present invention.

[0210] The above laminate includes two or more cured films, and is preferably in a form including a metal layer between any of the above cured films. The above metal layer is preferably formed by the above metal layer forming step.

[0211] As the above laminate, for example, a laminate having a layer structure including at least three layers of a first cured film, a metal layer, and a second cured film laminated in sequence can be cited as a preferred laminate.

[0212] Both the above-mentioned first cured film and the above-mentioned second cured film are preferably cured films obtained by the method for producing a cured film of the present invention. The photocurable resin composition of the present invention for forming the above-mentioned first cured film and the photocurable resin composition of the present invention for forming the above-mentioned second cured film may be compositions having the same composition or compositions having different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.

[0213] <Lamination step>

[0214] The method for producing a laminate of the present invention preferably includes a lamination step.

[0215] The lamination step is a series of steps including (a) a film formation step (layer formation step), (b) a first exposure step, (c) a development step, and (d) a second exposure step in this order on the surface of a cured film (resin layer) or a metal layer again. Among them, it may be a method of only repeating the film formation step of (a). And, a (e) metal layer formation step may be included after the (d) second exposure step. It goes without saying that the above-mentioned drying step, heating step, etc. can be appropriately further included in the lamination step.

[0216] When further performing a lamination step after the lamination step, a surface activation treatment step can be further performed after the above-mentioned first exposure step, after the above-mentioned second exposure step, or after the above-mentioned metal layer formation step. As the surface activation treatment, plasma treatment can be exemplified.

[0217] The above-mentioned lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and still more preferably 3 to 5 times.

[0218] For example, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, it is preferable to have a structure in which the resin layer is 2 or more layers and 20 or less layers, more preferably 3 or more layers and 7 or less layers, and still more preferably 3 or more layers and 5 or less layers.

[0219] In the present invention, especially after providing a metal layer, it is further preferable to form a cured film (resin layer) of the above-mentioned photocurable resin composition so as to cover the above-mentioned metal layer. Specifically, an example is a method of repeating in the order of (a) film formation step, (b) first exposure step, (c) development step, (d) second exposure step, and (e) metal layer formation step. By alternately performing the above-mentioned steps (a) to (d) for forming a cured film and the metal layer formation step, a cured film and a metal layer can be alternately laminated.

[0220] (Surface activation treatment step)

[0221] The method for manufacturing the laminate of the present invention may include a surface activation treatment step of performing a surface activation treatment on at least a part of the above metal layer and photosensitive resin composition layer.

[0222] The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step of performing a surface activation treatment on the photosensitive resin composition layer after the above exposure and development steps.

[0223] The surface activation treatment may be performed only on at least a part of the metal layer, only on at least a part of the exposed photosensitive resin composition layer, or on at least a part of both the metal layer and the exposed photosensitive resin composition layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and preferably on a part or all of the area of the metal layer where the photosensitive resin composition layer is formed on the surface. As described above, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin layer provided on its surface can be improved.

[0224] Moreover, the surface activation treatment is also preferably performed on a part or all of the exposed photosensitive resin composition layer (resin layer). As described above, by performing a surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion to the metal layer or resin layer provided on the surface subjected to the surface activation treatment can be improved.

[0225] As the surface activation treatment, specifically, it may be selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, surface treatment based on ultraviolet (UV) ozone method, treatment of dipping in hydrochloric acid aqueous solution to remove the oxide film and then dipping in an organic surface treatment agent containing at least one of an amino group and a thiol group, mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , most preferably 10,000 to 50,000 J / m 2 .

[0226] (Method for manufacturing an electronic device)

[0227] The present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured film of the present invention or a method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the photocurable resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Laid-Open No. 2016-027357, and these contents are incorporated into the present specification.

[0228] Hereinafter, the details of the photocurable resin composition used in the method for manufacturing a cured film of the present invention, the method for manufacturing a laminate of the present invention, or the method for manufacturing a semiconductor device of the present invention will be described.

[0229] (Photocurable resin composition)

[0230] The photocurable resin composition of the present invention is a photocurable resin composition used in the method for manufacturing a cured film of the present invention, the method for manufacturing a laminate of the present invention, or the method for manufacturing a semiconductor device of the present invention.

[0231] The first mode of the photocurable resin composition of the present invention includes at least one resin selected from the group consisting of polyimide and polybenzoxazole, a photosensitive compound A that is sensitive to the exposure wavelength in the first exposure step, and a photosensitive compound B that is not sensitive to the exposure wavelength in the first exposure step but is sensitive to the exposure wavelength in the second exposure step. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step, and the photocurable resin composition satisfies at least one of the following condition 1 and condition 2.

[0232] The second mode of the photocurable resin composition of the present invention is a photocurable resin composition that includes at least one resin selected from the group consisting of polyimide and polybenzoxazole, and photosensitive compounds A and B with a difference in maximum absorption wavelength of 80 nm or more. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the following first exposure step, and the photocurable resin composition satisfies at least one of the following condition 1 and condition 2, and is used in a method for manufacturing a cured film that includes a first exposure step of exposing a part of a photocurable film formed from the photocurable resin composition, a developing step of developing the exposed photocurable film with a developer to obtain a pattern, and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step.

[0233] Condition 1: The resin in the above photocurable resin composition contains a group that promotes a bonding reaction with other groups by the photosensitivity of the photosensitive compound B in the above second exposure step;

[0234] Condition 2: The above photocurable resin composition further contains a crosslinking agent having a group that promotes a bonding reaction with other groups by the photosensitivity of the photosensitive compound B in the above second exposure step.

[0235] The combination of the photosensitive compound A and the photosensitive compound B in the photocurable resin composition of the present invention is preferably any one of the following modes 1 to 7.

[0236] Mode 1: The photosensitive compound A is a photoinitiator for free radical polymerization, and the photosensitive compound B is a photoacid generator.

[0237] Mode 2: Both the photosensitive compound A and the photosensitive compound B are photoinitiators for free radical polymerization.

[0238] Mode 3: The photosensitive compound A is a photoinitiator for free radical polymerization, and the photosensitive compound B is a photo-base generator.

[0239] Mode 4: The photosensitive compound A is a photoacid generator, and the photosensitive compound B is a photoinitiator for free radical polymerization.

[0240] Mode 5: The photosensitive compound A is a photo-base generator, and the photosensitive compound B is a photoinitiator for free radical polymerization.

[0241] Mode 6: Both the photosensitive compound A and the photosensitive compound B are photoacid generators.

[0242] Mode 7: Both the photosensitive compound A and the photosensitive compound B are photo-base generators.

[0243] Among these, from the viewpoint of the resolution of the pattern, any one of Modes 1 to 4 is preferred.

[0244] From the viewpoint of the rectangularity of the pattern, Mode 1 is preferred.

[0245] From the viewpoint of solvent resistance, Mode 6 is preferred.

[0246] From the viewpoint of the film strength of the obtained cured film, Mode 4 is preferred.

[0247] From the viewpoint of being able to perform positive development of the photocurable film, Mode 4 is preferred.

[0248] From the viewpoint of having good stability (latitude) with respect to the exposure amount, Mode 2 is preferred.

[0249] <Mode 1>

[0250] In Mode 1, the photocurable resin composition preferably further contains a radical crosslinking agent and other crosslinking agents described below.

[0251] Moreover, in Mode 1, the specific resin contained in the photocurable resin may have a crosslinkable group described below or may not have a crosslinkable group described below. As the above crosslinkable group, it may be a radical polymerizable group described below or other crosslinkable groups described below.

[0252] Moreover, the photosensitive compound B in Mode 1 is preferably an onium salt compound or a sulfonate compound described below.

[0253] In the method for manufacturing the cured film of the present invention, when using the photocurable resin composition of Mode 1, radical polymerization is promoted in the exposed portion in the first exposure step, and acid-based crosslinking is promoted in the exposed portion in the second exposure step.

[0254] <Mode 2>

[0255] In Mode 2, the photocurable resin composition preferably further contains a radical crosslinking agent described below.

[0256] Moreover, in Mode 2, the specific resin contained in the photocurable resin may have a crosslinkable group described below or may not have a crosslinkable group described below. As the above crosslinkable group, it is preferably a radical polymerizable group described below.

[0257] In the method for manufacturing the cured film of the present invention, when using the photocurable resin composition of Mode 2, radical polymerization is promoted in the exposed portion in the first exposure step, and radical polymerization is also promoted in the exposed portion in the second exposure step.

[0258] <Mode 3>

[0259] In Mode 3, the photocurable resin composition preferably further contains a radical crosslinking agent and other crosslinking agents described below.

[0260] As the above other crosslinking agent, an epoxy compound is preferred.

[0261] Moreover, in Mode 3, the specific resin contained in the photocurable resin may have a crosslinkable group described below or may not have a crosslinkable group described below. As the above crosslinkable group, it is preferably a radical polymerizable group or an epoxy group described below.

[0262] In the method for manufacturing the cured film of the present invention, when using the photocurable resin composition of Mode 3, radical polymerization is promoted in the exposed portion in the first exposure step, and base-based crosslinking is promoted in the exposed portion in the second exposure step.

[0263] <Method 4>

[0264] In Method 4, the photocurable resin composition preferably further contains a radical crosslinking agent described later.

[0265] Moreover, in Method 4, the specific resin contained in the photocurable resin may or may not have a crosslinkable group described later. As the above crosslinkable group, a radical polymerizable group described later is preferred.

[0266] Moreover, the photosensitive compound A in Method 4 is preferably a quinonediazide compound described later.

[0267] In the method for producing a cured film of the present invention, when using the photocurable resin composition of Method 4, the solubility of the exposed portion in the developer is changed due to the generation of acid in the exposed portion in the first exposure step, and radical polymerization is promoted in the exposed portion in the second exposure step.

[0268] Moreover, it can also be designed such that by appropriately selecting a photoacid generator and a crosslinking agent as the photosensitive compound A, acid-based crosslinking is promoted in the exposed portion in the first exposure step, and radical polymerization is promoted in the exposed portion in the second exposure step.

[0269] <Method 5>

[0270] In Method 5, the photocurable resin composition preferably further contains a radical crosslinking agent described later and another crosslinking agent described later.

[0271] Moreover, in Method 5, the specific resin contained in the photocurable resin may or may not have a crosslinkable group described later. As the above crosslinkable group, it may be a radical polymerizable group described later or another crosslinkable group described later.

[0272] In the method for producing a cured film of the present invention, when using the photocurable resin composition of Method 5, base-based crosslinking is promoted in the exposed portion in the first exposure step, and radical polymerization is promoted in the exposed portion in the second exposure step.

[0273] <Methods 6 and 7>

[0274] In Method 6 or Method 7, the photocurable resin composition preferably further contains another crosslinking agent described later.

[0275] Moreover, in Method 6 or Method 7, the specific resin contained in the photocurable resin may or may not have a crosslinkable group described later. As the above crosslinkable group, another crosslinkable group described later is preferred.

[0276] In the method for manufacturing a cured film of the present invention, when using the photocurable resin composition of Mode 6, acid-based crosslinking is promoted in the exposed portion in the first exposure step, and acid-based crosslinking is also promoted in the exposed portion in the second exposure step.

[0277] In the method for manufacturing a cured film of the present invention, when using the photocurable resin composition of Mode 7, base-generation-based crosslinking is promoted in the exposed portion in the first exposure step, and base-generation-based crosslinking is also promoted in the exposed portion in the second exposure step.

[0278] Hereinafter, the details of each component contained in the photocurable resin composition of the present invention will be described.

[0279] <Specific resin>

[0280] The photocurable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide and polybenzoxazole.

[0281] The photocurable resin composition of the present invention preferably contains polyimide as the specific resin.

[0282] [Polyimide]

[0283] The polyimide used in the present invention is preferably a polyimide soluble in the above-described developer.

[0284] When the developer is an alkali developer, the polyimide is preferably an alkali-soluble polyimide. When the developer is an organic solvent, the polyimide is preferably a polyimide soluble in the organic solvent.

[0285] Being soluble in the developer means that 0.1 g or more of polyimide is dissolved in 100 g of the developer at 23°C. From the viewpoint of pattern formability, it is preferably 0.5 g or more of polyimide dissolved, and more preferably 1.0 g or more of polyimide dissolved. The upper limit of the above dissolution amount is not particularly limited, and is preferably 100 g or less.

[0286] Moreover, when the polyimide is an alkali-soluble polyimide, 0.1 g or more of polyimide is preferably dissolved in 100 g of 2.38 mass% tetramethylammonium hydroxide at 23°C. From the viewpoint of pattern formability, it is preferably 0.5 g or more of polyimide dissolved, and more preferably 1.0 g or more of polyimide dissolved. The upper limit of the above dissolution amount is not particularly limited, and is preferably 100 g or less.

[0287] Moreover, from the viewpoints of the film strength and insulation of the obtained cured film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0288] In this specification, the "main chain" refers to the relatively longest bonded chain in the molecule of the high molecular compound constituting the resin, and the "side chain" refers to the bonded chain other than that.

[0289] -Fluorine atom-

[0290] From the viewpoint of the film strength of the obtained cured film, the polyimide preferably has a fluorine atom.

[0291] The fluorine atom is preferably included, for example, in R in the repeating unit represented by the following formula (4). 132 Or R in the repeating unit represented by the following formula (4). 131 Among them, it is more preferably included as a fluorinated alkyl group in R in the repeating unit represented by the following formula (4). 132 Or R in the repeating unit represented by the following formula (4). 131 .

[0292] The amount of the fluorine atom relative to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.

[0293] -Silicon atom-

[0294] From the viewpoint of the film strength of the obtained cured film, the polyimide preferably has a silicon atom.

[0295] The silicon atom is preferably included, for example, in R in the repeating unit represented by the following formula (4). 131 , and more preferably included in R in the repeating unit represented by the following formula (4). 131 As the organic-modified (poly)siloxane structure described below.

[0296] Moreover, the above-mentioned silicon atom or the above-mentioned organic-modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.

[0297] The amount of the silicon atom relative to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

[0298] -Ethylenically unsaturated bond-

[0299] From the viewpoint of the film strength of the obtained cured film, the polyimide preferably has an ethylenically unsaturated bond.

[0300] The polyimide preferably has an ethylenically unsaturated group as a radically polymerizable group.

[0301] The group having the above-mentioned ethylenically unsaturated bond in the polyimide can be the group that promotes the bonding reaction with other groups by the photosensitization of the photosensitive compound B in the second exposure step under the above-mentioned condition 1.

[0302] Moreover, the group having the ethylenically unsaturated bond in the polyimide may be a group that promotes the bonding reaction with other groups by the photosensitization of the photosensitive compound A in the first exposure step.

[0303] The polyimide may have an ethylenically unsaturated bond at the main chain end or may have an ethylenically unsaturated bond in the side chain, and preferably has it in the side chain.

[0304] The above-mentioned ethylenically unsaturated bond preferably has radical polymerizability.

[0305] The ethylenically unsaturated bond preferably includes R in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4) 131 , and more preferably includes R in the repeating unit represented by the following formula (4) as the group having an ethylenically unsaturated bond 132 or R in the repeating unit represented by the following formula (4) 131 .

[0306] Among these, the ethylenically unsaturated bond preferably includes R in the repeating unit represented by the following formula (4) 131 , and more preferably includes R in the repeating unit represented by the following formula (4) 131 as the group having an ethylenically unsaturated bond.

[0307] Examples of the group having an ethylenically unsaturated bond include groups having a vinyl group that can be substituted and directly bonded to an aromatic ring, such as vinyl, allyl, vinylphenyl, (meth)acrylamide group, (meth)acryloyloxy group, and the group represented by the following formula (III).

[0308] [Chemical formula 1]

[0309]

[0310] In formula (III), R 200 represents a hydrogen atom or a methyl group, preferably a methyl group.

[0311] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)oxyalkylene group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the repeating number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group formed by combining two or more of these.

[0312] In addition, (poly)oxyalkylene represents oxyalkylene or polyoxyalkylene.

[0313] Among these, R 201 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

[0314] [Chemical formula 2]

[0315]

[0316] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)oxyalkylene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom to which R in formula (III) is bonded. 201 The bonding site of the oxygen atom to which it is bonded.

[0317] In formulas (R1) to (R3), the preferred forms of the alkylene group having 2 to 12 carbon atoms or the (poly)oxyalkylene group having 2 to 30 carbon atoms in L are the same as the preferred forms of the alkylene group having 2 to 12 carbon atoms or the (poly)oxyalkylene group having 2 to 30 carbon atoms in the above R 201 The same as the preferred form of the alkylene group having 2 to 12 carbon atoms or the (poly)oxyalkylene group having 2 to 30 carbon atoms in.

[0318] In formula (R1), X is preferably an oxygen atom.

[0319] In formulas (R1) to (R3), the meaning of * is the same as that of * in formula (III), and the preferred form is also the same.

[0320] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.).

[0321] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).

[0322] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

[0323] As the polyalkylene oxide, from the viewpoints of solvent solubility and solvent resistance, polyoxyethylene, polyoxypropylene, polytrimethylene oxide, polytetramethylene oxide, or a group in which a plurality of oxyethylene groups and a plurality of oxypropylene groups are bonded is preferred, polyoxyethylene or polyoxypropylene is more preferred, and polyoxyethylene is further preferred. In the group in which a plurality of oxyethylene groups and a plurality of oxypropylene groups are bonded, the oxyethylene groups and the oxypropylene groups may be randomly arranged, may form blocks and be arranged, or may be arranged in a pattern such as an alternating pattern. The preferred mode of the repetition number of oxyethylene groups and the like in these groups is as described above.

[0324] In formula (III), * represents a bonding site to other structures, and is preferably a bonding site to the main chain of the polyimide.

[0325] The amount of the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0326] And, from the viewpoint of manufacturing suitability, the amount of the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0327] -Crosslinkable group other than ethylenically unsaturated bond-

[0328] The polyimide may have a crosslinkable group (other crosslinkable group) other than the ethylenically unsaturated bond.

[0329] The crosslinkable group other than the above-mentioned ethylenically unsaturated bond in the polyimide may be a group that promotes the bonding reaction with other groups by the exposure of the photosensitive compound B in the second exposure step under the above condition 1.

[0330] And, the crosslinkable group other than the above-mentioned ethylenically unsaturated bond in the polyimide may be a group that promotes the bonding reaction with other groups by the exposure of the photosensitive compound A in the first exposure step.

[0331] Examples of the crosslinkable group other than the ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0332] The crosslinkable group other than the ethylenically unsaturated bond preferably includes R in the repeating unit represented by formula (4) described later. 131 .

[0333] The amount of the crosslinkable group other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0334] Further, from the viewpoint of manufacturing suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0335] -Polarity conversion group-

[0336] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate a base-soluble group such as a phenolic hydroxyl group or a carboxyl group, and is preferably an acetal group, a ketal group, a silicon group, a silicon ether group, a tertiary alkyl ester group, etc. From the viewpoint of exposure sensitivity, an acetal group is more preferable.

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

[0338] -Acid value-

[0339] When the polyimide is used for alkali development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more.

[0340] Further, the above acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and further preferably 200 mgKOH / g or less.

[0341] Further, when the polyimide is used in development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and further preferably 5 to 20 mgKOH / g.

[0342] The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0343] Further, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of preferably 0 to 10, more preferably 3 to 8 is used.

[0344] pKa refers to the dissociation reaction of an acid releasing hydrogen ions, and its equilibrium constant Ka is represented by the negative common logarithm pKa. In this specification, unless otherwise specified, the pKa is set to the calculated value based on ACD / ChemSketch (registered trademark). Alternatively, the values described in "Revised 5th Edition Chemical Handbook Basic Volume" edited by the Chemical Society of Japan can be referred to.

[0345] Moreover, when the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0346] As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0347] -Phenolic hydroxyl group-

[0348] From the viewpoint of making the development rate based on an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0349] The polyimide may have a phenolic hydroxyl group at the main chain end or may have a phenolic hydroxyl group in the side chain.

[0350] The phenolic hydroxyl group preferably contains, for example, R in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4) 131 .

[0351] The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0352] -Repeating unit represented by formula (4)-

[0353] As the polyimide used in the present invention, as long as it is a high molecular compound having an imide ring, there is no particular limitation. It preferably contains a repeating unit represented by the following formula (4), and more preferably a compound containing a repeating unit represented by formula (4) and having a crosslinkable group.

[0354] As the crosslinkable group, the above-mentioned group having an ethylenically unsaturated bond or a crosslinkable group other than the ethylenically unsaturated bond can be cited.

[0355] [Chemical formula 3]

[0356]

[0357] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.

[0358] When the polyimide has a crosslinkable group, the crosslinkable group may be located on at least one of R 131 and R 132 , or as shown in the following formula (4-1) or formula (4-2), it may be located at the end of the polyimide.

[0359] Formula (4-1)

[0360] [Chemical formula 4]

[0361]

[0362] In formula (4-1), R 133 is a group having a crosslinkable group, and the meanings of other groups are the same as those in formula (4).

[0363] Formula (4-2)

[0364] [Chemical formula 5]

[0365]

[0366] R 134 and R 135 at least one of them is a group having a crosslinkable group, and when it is a group without a crosslinkable group, it is an organic group, and the meanings of other groups are the same as those in formula (4).

[0367] <<R 131 >>

[0368] R 131 represents a divalent organic group. As the divalent organic group, groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups can be exemplified. Preferably, they are linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 6 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups composed of combinations of these. More preferably, they are groups containing aromatic groups having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, the case of a group represented by -Ar-L-Ar- can be exemplified. Among them, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of combinations of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0369] R 131Preferably derived from diamines. Examples of diamines used for producing polyimide include linear or branched aliphatic, cycloaliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds may be used.

[0370] Specifically, preferred are diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof, and more preferred are diamines containing a group composed of an aromatic group having 6 to 20 carbon atoms. Examples of the group containing an aromatic group include the following groups. In the following formulas, * each independently represents a bonding site to other structures.

[0371] [Chemical formula 6]

[0372]

[0373] In the formula, A is preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, and NHCO-, and a group selected from a combination thereof, more preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, and further preferably a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -C(CF3)2- and -C(CH3)2-.

[0374] In the formula, R 1 ~R 3 each independently represents a hydrogen atom or a substituent, preferably a group having a hydrogen atom, a hydrocarbon group or a crosslinkable group, more preferably a hydrogen atom, an epoxypropyl group or a group represented by the following formula (E1).

[0375] [Chemical formula 7]

[0376]

[0377] In formula (E1), R E1 represents a hydrogen atom or a methyl group, preferably a methyl group.

[0378] In formula (E1), X represents -O- or -NR N -. R N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom or a methyl group.

[0379] In formula (E1), R E2represents a divalent linking group, preferably an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)oxyalkylene group having 2 to 30 carbon atoms (the carbon atoms of the alkylene group are preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the repeating number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group formed by combining two or more of these, and more preferably an alkylene group having 2 to 12 carbon atoms.

[0380] In formula (E1), * represents a bonding site to other structures.

[0381] As the diamine, specifically, examples thereof include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl, or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-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)-10H-anthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,At least one diamine selected from 9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene, 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, diester of dibenzoic acid, 1,5-dinaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)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'-hexafluorobiphenylamine and 4,4'-diaminotetraphenylbenzene.,

[0382] Also preferred are the following diamines (DA-1) to (DA-18).

[0383] [Chemical formula 8]

[0384]

[0385] [Chemical formula 9]

[0386]

[0387] Further, as a preferred example, diamines having at least two alkylene glycol units in the main chain can also be mentioned. More preferably, diamines that collectively contain either one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and even more preferably the above-mentioned diamines (diamines that do not contain an aromatic ring). As specific examples, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc. can be mentioned, but are not limited to these.

[0388] The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[0389] [Chemical formula 10]

[0390]

[0391] In the above, x, y, and z are average values.

[0392] From the viewpoint of the flexibility of the obtained cured film, R 131 is preferably represented by -Ar-L-Ar-. Among them, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or NHCO-, or a group composed of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0393] Further, from the viewpoint of the i-ray transmittance, R 131 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-ray transmittance and easy availability, a divalent organic group represented by formula (61) is more preferred.

[0394] Formula (51)

[0395] [Chemical formula 11]

[0396]

[0397] In formula (51), R 50 ~R57 Each independently represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to other structures.

[0398] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[0399] [Chemical formula 12]

[0400]

[0401] In formula (61), R 58 and R 59 Each independently represents a fluorine atom or a trifluoromethyl group. * Each independently represents a bonding site to other structures.

[0402] Examples of the diamine compound for imparting the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. These can be used alone or in combination of two or more.

[0403] In addition, the following diamines can also be preferably used.

[0404] [Chemical formula 13]

[0405]

[0406] <<R 132 >>

[0407] R 132 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In the following formulas (5) and (6), * each independently represents a bonding site to other structures.

[0408] [Chemical formula 14]

[0409]

[0410] In formula (5), R 112Preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO- or a group represented by a combination of these, more preferably a group selected from the group consisting of a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and -SO2-, and still more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and SO2-.

[0411] Specifically, R 132 Examples include a tetracarboxylic acid residue remaining after removing the acid anhydride group from a tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds may be used.

[0412] The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0413] [Chemical formula 15]

[0414]

[0415] In formula (O), R 115 represents a tetravalent organic group. The meaning of the preferred range of R 115 is the same as that of R 132 in formula (4), and the preferred ranges are also the same.

[0416] As specific examples of the tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 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, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2’,3,3’-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof may be mentioned.

[0417] Furthermore, as preferred examples, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) may also be mentioned.

[0418] [Chemical formula 16]

[0419]

[0420] It is also preferred that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) may be mentioned as preferred examples. As R 132 , the above (DAA-1) to (DAA-5) may be mentioned as more preferred examples.

[0421] Further, in order to improve the storage stability of the composition, the polyimide preferably has the main chain terminals sealed with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloroacyl compound, a monoactive ester compound, etc. Among these, a monoamine is more preferably used. Preferred compounds as the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, etc. Two or more of these can be used, and a variety of different terminal groups can also be introduced by reacting a plurality of capping agents.

[0422] -Imidization rate (ring closure rate)-

[0423] From the viewpoints of the film strength, insulation property, etc. of the obtained cured film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

[0424] The upper limit of the above imidization rate is not particularly limited, and it may be 100% or less.

[0425] For example, the above imidization rate can be measured by the following method.

[0426] Measure the infrared absorption spectrum of the polyimide, and obtain the peak intensity P1 of the absorption peak derived from the imide structure, i.e., the peak around 1377 cm -1 . Then, after heat-treating the polyimide at 350 °C for 1 hour, measure the infrared absorption spectrum again, and obtain the peak intensity P2 of the peak around 1377 cm -1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be obtained according to the following formula.

[0427] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0428] The polyimide may include all containing one kind of R 131 or R 132The repeating unit of the above formula (4) may also include two or more different types of R 131 or R 132 The repeating unit of the above formula (4). In addition to the repeating unit of the above formula (4), the polyimide may also contain other types of repeating units.

[0429] For example, polyimide can be obtained by a method of reacting a tetracarboxylic dianhydride with a diamine compound (with a part substituted by a monoamine, i.e., a capping agent) at low temperature, a method of reacting a tetracarboxylic dianhydride (with a part substituted by an acid anhydride or a monoacyl chloride compound or a monoactive ester compound, i.e., a capping agent) with a diamine compound at low temperature, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine (with a part substituted by a monoamine, i.e., a capping agent) and a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then acyl chlorinating the remaining dicarboxylic acid and reacting it with a diamine (with a part substituted by a monoamine, i.e., a capping agent), etc. The polyimide precursor is obtained, and it is synthesized by a known imidization reaction method, using a method of complete imidization or a method of stopping the imidization reaction midway and introducing a part of the imide structure, and further by a method of introducing a part of the imide structure by mixing a completely imidized polymer and its polyimide precursor.

[0430] Examples of commercially available polyimides include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation).

[0431] -Capping agent-

[0432] When manufacturing polyimide or polyimide precursor, etc., in order to further improve the storage stability, it is preferable to seal the ends of the polyimide precursor, etc. with a capping agent such as an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoactive ester compound, etc. As the capping agent, it is more preferable to use a monoalcohol, a phenol, a thiol, a benzenethiol, a monoamine.

[0433] Preferred compounds as monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tert-butyl alcohol, adamantanol, etc. Preferred compounds as phenols include phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, etc.

[0434] Preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting multiple capping agents.

[0435] Moreover, when sealing the amino group at the end of the sealing resin, it can be sealed with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for the amino group are preferably carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic carboxylic anhydrides, etc., and more preferably carboxylic anhydrides and carboxylic acid chlorides. Preferred compounds as carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, etc. Moreover, preferred compounds as carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl, benzoyl chloride, etc.

[0436] -Solid precipitation-

[0437] When manufacturing polyimide, etc., it may include a step of precipitating a solid. Specifically, by precipitating polyimide, etc. in the reaction solution in water and dissolving it in a solvent capable of dissolving polyimide, etc., such as tetrahydrofuran, solid precipitation can be carried out.

[0438] After that, by drying polyimide, etc., powdery polyimide, etc. can be obtained.

[0439] Regarding the weight-average molecular weight (Mw) of the polyimide, it may be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or more, the bend resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. Further, when two or more polyimides are contained, it is preferable that the weight-average molecular weight of at least one polyimide is within the above range.

[0440] 〔Polyphenylene Oxazole〕

[0441] As the polyphenylene oxazole, there is no particular limitation as long as it is a high molecular compound having a benzoxazole ring, and a compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a crosslinkable group is more preferred.

[0442] [Chemical formula 17]

[0443]

[0444] In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group.

[0445] When having a crosslinkable group, the crosslinkable group may be located on at least one of R 133 and R 134 , or as shown in the following formula (X-1) or formula (X-2), may be located at the end of the polyphenylene oxazole.

[0446] Formula (X-1)

[0447] [Chemical formula 18]

[0448]

[0449] In formula (X-1), at least one of R 135 and R 136 is a group having a crosslinkable group, and when it is a group without a crosslinkable group, it is an organic group, and the meanings of the other groups are the same as those in formula (X).

[0450] Formula (X-2)

[0451] [Chemical formula 19]

[0452]

[0453] In formula (X-2), R 137is a group having a crosslinkable group, and the others are substituents. The meanings of the other groups are the same as those in formula (X).

[0454] The meaning of the crosslinkable group in polybenzoxazole is the same as the crosslinkable group described as the crosslinkable group possessed by the above polyimide.

[0455] The above crosslinkable group in polybenzoxazole may be a group that promotes the bonding reaction with other groups by the photosensitivity of the photosensitive compound B in the second exposure step under the above condition 1.

[0456] Furthermore, the above crosslinkable group in polybenzoxazole may be a group that promotes the bonding reaction with other groups by the photosensitivity of the photosensitive compound A in the first exposure step.

[0457] <<R 133 >>

[0458] R 133 represents a divalent organic group. As the divalent organic group, it is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferred. R 133 is preferably a dicarboxylic acid residue. Only one kind of dicarboxylic acid residue may be used, or two or more kinds may be used.

[0459] As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.

[0460] As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.

[0461] Examples of the dicarboxylic acid containing an aliphatic group having a straight chain include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula, etc.

[0462] [Chemical formula 20]

[0463]

[0464] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0465] As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid composed only of the following aromatic group and two -COOH groups is more preferred.

[0466] [Chemical formula 21]

[0467]

[0468] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-.

[0469] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0470] <<R 134 >>

[0471] In formula (X), R 134 represents a tetravalent organic group. As the tetravalent organic group, the meaning is the same as that of R in the above formula (4), and the preferred range is also the same. 132 Same

[0472] And, R 134 is preferably a group derived from a diaminophenol derivative. As the group derived from a diaminophenol derivative, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. can be mentioned. These diaminophenols can be used alone or in combination.

[0473] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic group are preferred.

[0474] [Chemical formula 22]

[0475]

[0476] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2- or -NHCO-.

[0477] [Chemical formula 23]

[0478]

[0479] In formula (A-s), R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond or an organic group selected from the group of the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, a cyclic alkyl group, and they may be the same or different. R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, a cyclic alkyl group, and they may be the same or different.

[0480] [Chemical formula 24]

[0481]

[0482] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the diaminophenol derivative represented by the above formula (A-s).)

[0483] In the above formula (A-s), it is considered that when there is also a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, the distance between the carbonyl carbon of the amide bond and the hydroxyl group becomes closer, and from the viewpoint of further improving the effect of increasing the cyclization rate during curing at low temperatures, it is particularly preferred.

[0484] Moreover, in the above formula (A-s), when R2 is an alkyl group and R3 is an alkyl group, it is possible to maintain high transparency to i-rays and the effect of a high cyclization rate during curing at low temperatures, and thus it is preferred.

[0485] Furthermore, in the above formula (A-s), R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group related to R1 include -CH2-, -CH(CH3)-, -C(CH3)2-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH2CH3)(CH2CH3)-, -CH(CH2CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -CH(CH(CH3)2)-, -C(CH3)(CH(CH3)2)-, -CH(CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH3)-, -CH(CH2CH(CH3)2)-, -C(CH3)(CH2CH(CH3)2)-, -CH(CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH3)-, -CH(CH2CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH2CH3)-, etc. Among them, from the viewpoint of obtaining a polybenzoxazole precursor with excellent balance that can maintain high transparency to i-rays and a high cyclization rate during curing at low temperatures while having sufficient solubility in solvents, -CH2-, -CH(CH3)-, -C(CH3)2- are more preferred.

[0486] As a method for producing the diaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506, and these contents are incorporated into this specification.

[0487] Specific examples of the structure of the diaminophenol derivative represented by the above formula (A-s) include the contents described in paragraphs 0070 to 0080 of Japanese Patent Application Laid-Open No. 2013-256506, and these contents are incorporated into this specification. Of course, it is not limited to these.

[0488] In addition to the repeating units of the above formula (X), polybenzoxazole may also contain other types of repeating units.

[0489] From the viewpoint of being able to suppress warping accompanying the formation of the closed loop, it is preferable to contain a diamine residue represented by the following formula (SL) as other types of repeating units.

[0490] [Chemical formula 25]

[0491]

[0492] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms, and R 3s , R 4s , R 5s , R 6s at least one of them is an aromatic group, and the remaining part is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and they may be the same or different respectively. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

[0493] In formula (SL), as a preferable Z, examples of R 5s and R 6s in the b structure being phenyl can be cited. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.

[0494] When containing a diamine residue represented by formula (SL) as other types of repeating units, it is further preferable to contain a tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride as a repeating unit. As an example of such a tetracarboxylic acid residue, an example of R 132 in formula (4) can be cited.

[0495] For example, a polybenzoxazole precursor is obtained by reacting a bisaminophenol derivative with a compound such as a dicarboxylic acid containing R 133 or a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the above dicarboxylic acids, and subjecting it to oxazolization using a known oxazolization reaction method, whereby polybenzoxazole can be obtained.

[0496] In addition, in the case of a dicarboxylic acid, in order to improve the reaction yield, etc., an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like can also be used.

[0497] Further, in the synthesis of polybenzoxazole or a polybenzoxazole precursor, the above-mentioned end-capping agent can be used in the same manner as in the synthesis of the above-mentioned polyimide or polyimide precursor, and solid precipitation can also be carried out in the same manner as in the synthesis of the above-mentioned polybenzoxazole precursor.

[0498] The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or more, the bend resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. Further, when two or more polybenzoxazoles are contained, the weight-average molecular weight of at least one polybenzoxazole is preferably within the above range.

[0499] 〔Content〕

[0500] The content of the specific resin in the photocurable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the photocurable resin composition. Further, the content of the specific resin in the photocurable resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, yet more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the photocurable resin composition.

[0501] The photocurable resin composition of the present invention may contain only one kind of specific resin or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0502] <Other resins>

[0503] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0504] Examples of the other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.

[0505] For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a pattern (cured film) having excellent solvent resistance can also be obtained.

[0506] For example, by adding, instead of or in addition to the polymerizable compound described below, a highly priced acrylic resin having a polymerizable group with a weight average molecular weight of 20,000 or less to the composition, the coatability of the composition, the solvent resistance of the pattern (cured film), etc. can be improved.

[0507] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the composition.

[0508] Moreover, the content of the other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total solid content of the composition.

[0509] Also, as a preferred mode of the resin composition of the present invention, a mode with a low content of other resins can also be adopted. In the above mode, the content of the other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, still more preferably 1% by mass or less, based on the total solid content of the composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0510] The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0511] <Photosensitive Compound A>

[0512] In the first mode of the method for manufacturing the cured film of the present invention, the photocurable resin composition contains a photosensitive compound A that is sensitive to the exposure wavelength in the above-described first exposure step.

[0513] Whether the photosensitive compound is sensitive to the exposure wavelength in the first exposure step can be determined by the following method.

[0514] Dissolve the photosensitive compound and polymethyl methacrylate (PMMA) in methyl ethyl ketone to prepare a composition for forming a mold film. The content of the photosensitive compound in the composition for forming a mold film is set to 0.5 mmol / g based on the total mass of the photosensitive compound A and PMMA. Moreover, the amount of methyl ethyl ketone used in the composition for forming a mold film can be appropriately set according to the film thickness of the mold film described below.

[0515] Moreover, the weight-average molecular weight of PMMA was set to 10,000.

[0516] Thereafter, the obtained composition for forming a mold film was coated on glass and heat-dried at 80°C for 1 minute to obtain a mold film. The film thickness of the mold film was made 10 μm. Thereafter, using the same light source as the exposure in the first exposure step, the composition film was exposed at the same wavelength and exposure dose as the above exposure.

[0517] After the above exposure, while applying ultrasonic waves to a methanol / THF = 50 / 50 (mass ratio) solution, the above mold film and the glass on which the above mold film was formed were immersed in this solution for 10 minutes. The extract extracted into the above solution was analyzed by HPLC (high performance liquid chromatography), and thus the residual ratio of the photosensitive compound was calculated using the following formula.

[0518] Residual ratio of photosensitive compound (%) = amount of photosensitive compound contained in the mold film after exposure (mol) / content of photosensitive compound contained in the mold film before exposure (mol) × 100

[0519] Moreover, when the residual ratio of the above photosensitive compound is less than 80%, it is determined that the above photosensitive compound is a compound sensitive to the exposure wavelength in the first exposure step. The above residual ratio is preferably 70% or less, more preferably 60% or less, and further preferably 50% or less. The lower limit of the above residual ratio is not particularly limited and can be 0%.

[0520] When the residual ratio of the above photosensitive compound is 80% or more, it is determined that the above photosensitive compound is a compound not sensitive to the exposure wavelength in the first exposure step. The above residual ratio is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The upper limit of the above residual ratio is not particularly limited and can be 100%.

[0521] The photosensitive compound A may or may not be sensitive to the exposure wavelength in the second exposure step. From the viewpoints of the film strength and solvent resistance of the obtained cured film, it is preferably sensitive to the exposure wavelength in the second exposure step.

[0522] Regarding whether it is sensitive to the exposure wavelength in the second exposure step, in the determination method for whether it is sensitive to the exposure wavelength in the first exposure step, it can be determined by a determination method in which the description of "the first exposure step" is replaced with the description of "the second exposure step".

[0523] In the second aspect of the method for manufacturing the cured film of the present invention, the difference between the maximum absorption wavelength of the photosensitive compound A and the maximum absorption wavelength of the photosensitive compound B is 80 nm or more, preferably 90 to 300 nm, and more preferably 100 to 200 nm.

[0524] The maximum absorption wavelength of the photosensitive compound A is preferably 190 to 450 nm, and more preferably 320 to 450 nm.

[0525] Moreover, the maximum absorption wavelength of the photosensitive compound A is preferably greater than the maximum absorption wavelength of the photosensitive compound B.

[0526] The maximum absorption wavelength of the photosensitive compound is defined as the wavelength on the longest wavelength side among the maximum absorption wavelengths in the wavelength range of 190 to 500 nm.

[0527] The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step.

[0528] Specifically, the photosensitive compound A is preferably a compound having a chemical change (generation of free radicals, generation of acids, etc.) through the first exposure step and changing the solubility of the photocurable layer in the developer accompanying the above structural change, and more preferably a compound that generates free radicals through the first exposure step.

[0529] Moreover, the photosensitive compound A is preferably a photoinitiator or a photoacid generator.

[0530] 〔Photoinitiator〕

[0531] Examples of the photoinitiator include a photo radical polymerization initiator, a photo cationic polymerization initiator, etc., and a photo radical polymerization initiator is preferred.

[0532] The photo radical polymerization initiator is a compound that meets the above compound that generates free radicals through the first exposure step.

[0533] - Photo radical polymerization initiator -

[0534] The photocurable resin composition of the present invention preferably contains a photo radical polymerization initiator as the photosensitive compound A.

[0535] For example, by the photocurable resin composition containing a photo radical polymerization initiator and at least one of a specific resin having a radically polymerizable ethylenically unsaturated bond and a radical crosslinking agent described later, radical polymerization is carried out, and the solubility of the exposed portion of the photocurable layer in the developer decreases, so that a negative pattern can be formed.

[0536] As the photo radical polymerization initiator, there is no particular limitation, and it can be appropriately selected from known compounds, for example. For example, a photo radical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. Also, it can be an active agent that interacts with a photoexcited sensitizer to generate active radicals.

[0537] The photo radical generator preferably contains at least one compound having a molar extinction coefficient of at least about 50 L / mol / cm for light having a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). -1 / cm -1 The molar extinction coefficient of the compound can be measured by a known method. For example, it is preferably measured at a concentration of 0.01 g / L using ethyl acetate as a solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

[0538] As the photo radical polymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (such as compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminophenylethanone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron-arene complexes, etc. For the detailed content of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Laid-Open No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and these contents are incorporated into this specification.

[0539] As the ketone compound, for example, the compounds described in paragraph 0087 of Japanese Patent Laid-Open No. 2015-087611 can be exemplified, and this content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0540] As the photo radical polymerization initiator, hydroxyacetophenone compounds, aminophenylethanone compounds, and acylphosphine compounds can also be preferably used. More specifically, for example, the aminophenylethanone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can also be used.

[0541] As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used.

[0542] As the aminobenzophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resins B.V.) can be used.

[0543] As the aminobenzophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179, whose absorption maximum wavelength matches a light source wavelength such as 365 nm or 405 nm, can also be used.

[0544] Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-oxide phosphine, etc. Also, commercially available products such as IRGACURE-819 or IRGACURE-TPO (trade names: all manufactured by BASF Corporation), Omnirad 819 or Omnirad TPO (all manufactured by IGM Resins B.V.) can be used.

[0545] Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation), etc.

[0546] As the photo radical polymerization initiator, an oxime compound is more preferably cited. By using the oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is wide, and it also functions as a photo-curing accelerator, so it is particularly preferred.

[0547] As specific examples of the oxime compound, the compounds described in Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Laid-Open No. 2000-080068, and Japanese Patent Laid-Open No. 2006-342166 can be used.

[0548] As preferred oxime compounds, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyimino pentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. can be cited. In the photocurable resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is particularly preferably used as a photo radical polymerization initiator. The oxime compound as a photo radical polymerization initiator has a linking group represented by >C=N-O-C(=O)- in the molecule.

[0549] [Chemical formula 26]

[0550]

[0551] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photo radical polymerization initiator 2 described in Japanese Unexamined Patent Application Publication No. 2012-014052) can also be preferably used. And, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. And, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. And, oxime compounds having the following structures can also be used.

[0552] [Chemical formula 27]

[0553]

[0554] As a photo polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in Japanese Unexamined Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081.

[0555] As the photoinitiator, an oxime compound in which at least one benzene ring having a carbazole ring is a naphthalene ring skeleton can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013 / 083505.

[0556] An oxime compound having a fluorine atom can also be used. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, the compound (C-3) described in paragraph 0101 of JP-A-2013-164471, and the like.

[0557] As the most preferred oxime compound, an oxime compound having a specific substituent shown in JP-A-2007-269779, an oxime compound having a thioaryl group shown in JP-A-2009-191061, or the like can be mentioned.

[0558] From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivatives, a cyclopentadienyl-benzene-iron complex and its salt, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

[0559] More preferred photo radical polymerization initiators are a trihalomethyltriazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, and an acetophenone compound. Further preferably, it is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. More preferably, a metallocene compound or an oxime compound is used, and still more preferably, an oxime compound is used.

[0560] Further, as the photo radical polymerization initiator, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, quinones formed by fusing with an aromatic ring such as 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 can also be used. Further, the compound represented by the following formula (I) can also be used.

[0561] [Chemical formula 28]

[0562]

[0563] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II), or is the same group as R I00 , and R I02 to R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0564] [Chemical formula 29]

[0565]

[0566] In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

[0567] Further, as the photo radical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used.

[0568] When the photocurable resin composition contains a photo radical polymerization initiator, the content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photocurable resin composition of the present invention. The photo radical polymerization initiator may contain only one kind or two or more kinds. When two or more kinds of photo radical polymerization initiators are contained, it is preferred that their total is within the above range.

[0569] - Photoacid generator -

[0570] The photocurable resin composition of the present invention also preferably contains a photoacid generator as the photosensitive compound A.

[0571] By containing a photoacid generator, for example, an acid is generated in the exposed portion of the photocurable layer, and the solubility in the developer (for example, an aqueous alkali solution) of the above-mentioned exposed portion is increased, and a positive relief pattern in which the exposed portion is removed by the developer can be obtained.

[0572] Moreover, it can also be set in the following manner: by the photocurable resin composition containing a photoacid generator and a crosslinking agent described later, for example, the crosslinking reaction of the crosslinking agent is promoted by the acid generated in the exposed portion, and the exposed portion is less likely to be removed by the developer than the non-exposed portion. According to this method, a negative relief pattern can be obtained.

[0573] The photoacid generator is not particularly limited as long as it generates an acid upon exposure, and examples thereof include quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts and other onium salt compounds, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyl sulfonates and other sulfonate compounds.

[0574] Examples of the quinonediazide compound include a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester, a compound in which a sulfonic acid of quinonediazide is subjected to a sulfonamide bond with a polyamino compound, a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferred that 50 mol% or more of the entire functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

[0575] In the present invention, as the quinone diazide, 5-naphthoquinone diazidosulfonyl group or 4-naphthoquinone diazidosulfonyl group can be preferably used. The 4-naphthoquinone diazidosulfonate compound has absorption in the i-ray region of a mercury lamp, and thus is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazidosulfonate compound extends to the g-ray region of the mercury lamp, and thus is suitable for g-ray exposure. In the present invention, according to the wavelength of exposure, the 4-naphthoquinone diazidosulfonate compound or the 5-naphthoquinone diazidosulfonate compound is preferably selected. Moreover, a naphthoquinone diazidosulfonate compound having both a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazidosulfonate compound and a 5-naphthoquinone diazidosulfonate compound may be contained.

[0576] The above-mentioned naphthoquinone diazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazidosulfoxide compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.

[0577] Examples of the onium salt compound or sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

[0578] The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").

[0579] The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, and an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later is preferred.

[0580] [Chemical formula 30]

[0581]

[0582] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are a plurality of X 3 , they may be the same or different from each other. The alkyl group and the alkoxy group in the above-mentioned X 3 may have substituents. As the alkyl group in the above-mentioned X 3 , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in the above-mentioned X 3 , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above-mentioned X 3 , a chlorine atom or a fluorine atom is preferred.

[0583] In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 may be the same or different.

[0584] In formula (OS-1), R 34 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W, or an anthranilic acid group which may be substituted by W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0585] In formula (OS-1), when m3 is 3, X 3 is methyl, and the substitution position of X 3 is the ortho position, and R 34 is particularly preferably a compound having a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornane methyl group, or p-tolyl group.

[0586] As specific examples of the oxime sulfonate compound represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674 can be exemplified, and these are incorporated herein.

[0587] [Chemical formula 31]

[0588]

[0589] In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group. When there are multiple Rs, some of them s2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. When there are multiple Rs, some of them s6 each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, a sulfamoyl group, or an alkoxysulfonyl group. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6.

[0590] In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent T.

[0591] In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. When there are two or more in the compound, some Rs s2 are preferably one or two being an alkyl group, an aryl group or a halogen atom, more preferably one being an alkyl group, an aryl group or a halogen atom, and particularly preferably one being an alkyl group and the rest being hydrogen atoms. The alkyl group or aryl group represented by R s2 may have a substituent T.

[0592] In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0593] In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0594] In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R s6 may have a substituent.

[0595] In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0596] Moreover, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).

[0597] [Chemical formula 32]

[0598]

[0599] In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R t2 represents a hydrogen atom or a methyl group.

[0600] In the formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

[0601] In the formulas (OS-106) to (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0602] In the formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.

[0603] R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0604] Moreover, regarding the stereostructure (E, Z) of the oxime, it may be any one of the above-mentioned oxime sulfonate compounds or a mixture.

[0605] As specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Laid-Open No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Laid-Open No. 2015-194674 are exemplified, and these contents are incorporated into the present specification.

[0606] As a preferred other mode of the oxime sulfonate compound containing at least one oxime sulfonate group, the compounds represented by the following formulas (OS-101) and (OS-102) can be cited.

[0607] [Chemical formula 33]

[0608]

[0609] In the formula (OS-101) or the formula (OS-102), R u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. R u9More preferably in the form of a cyano group or an aryl group, R u9 Even more preferably in the form of a cyano group, a phenyl group or a naphthyl group.

[0610] In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group.

[0611] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H-, or CR u6 R u7 -, R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0612] In formula (OS-101) or formula (OS-102), R u1 ~R u4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R u1 ~R u4 can be bonded to each other to form a ring. At this time, the ring can be fused to form a fused ring together with the benzene ring. As R u1 ~R u4 , it is preferably a hydrogen atom, a halogen atom or an alkyl group, and it is also preferably a form in which at least two of R u1 ~R u4 are bonded to each other to form an aryl group. Among them, R u1 ~R u4 are all preferably in the form of hydrogen atoms. The above substituents can all further have substituents.

[0613] The compound represented by the above formula (OS-101) is more preferably the compound represented by formula (OS-102).

[0614] Moreover, regarding the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring, it can be any one of the above oxime sulfonate compounds, or a mixture.

[0615] As specific examples of the compound represented by formula (OS-101), the compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraphs 0195 to 0207 of JP-A-2015-194674 can be exemplified, and these are incorporated herein.

[0616] Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

[0617] In addition, commercially available products can be used as the photoacid generator. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (both manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like.

[0618] Moreover, compounds represented by the following structural formulas can also be preferably exemplified.

[0619] [Chemical formula 34]

[0620]

[0621] Organic halogen compounds can also be used as the photoacid generator. Specific examples of the organic halogen compounds include the compounds described in Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Application Publication No. 48-36281, Japanese Unexamined Patent Application Publication No. 55-32070, Japanese Unexamined Patent Application Publication No. 60-239736, Japanese Unexamined Patent Application Publication No. 61-169835, Japanese Unexamined Patent Application Publication No. 61-169837, Japanese Unexamined Patent Application Publication No. 62-58241, Japanese Unexamined Patent Application Publication No. 62-212401, Japanese Unexamined Patent Application Publication No. 63-70243, Japanese Unexamined Patent Application Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970), etc. Particularly, oxazole compounds substituted with a trihalomethyl group and S-triazine compounds can be exemplified.

[0622] More preferably, it is an s-triazine derivative in which at least one monohalogen-substituted methyl, dihalogen-substituted methyl or trihalogen-substituted methyl is bonded to the s-triazine ring. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-butyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-naphthoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc. can be cited.

[0623] As a photoacid generator, an organic borate compound can also be used. As the organic borate compound, for example, organic borates described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998, Chicago", etc., organic sulfonium borate complexes or organic oxosulfonium borate complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, organic iodine borate complexes described in JP-A-6-175554, JP-A-6-175553, organic phosphonium borate complexes described in JP-A-9-188710, organic boron transition metal coordination complexes in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. can be cited as specific examples.

[0624] As a photoacid generator, a disulfone compound can also be used. As the disulfone compound, compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, etc., and diazo disulfone compounds can be cited.

[0625] As the above-mentioned onium salts, for example, diazonium salts described in S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, iodonium salts described in the specifications of European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, sulfonium salts described in the specifications of European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, selenonium salts described in J.V. Crivello et al, Macromolecules, 10(6), 1307 (1977), J.V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsonium salts described in C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), pyridinium salts and other onium salts, etc.

[0626] As the onium salts, onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited.

[0627] [Chemical formula 35]

[0628]

[0629] In formula (RI-I), Ar 11represents an aryl group having 1 to 6 substituents and having 20 or less carbon atoms. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, a thioaryl group having 1 to 12 carbon atoms. Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion. From the viewpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion are preferred. In formula (RI-II), Ar 21 、Ar 22 represents an aryl group having 1 to 6 substituents and having 20 or less carbon atoms, which may be the same or different. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, a thioaryl group having 1 to 12 carbon atoms. Z 21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion. From the viewpoints of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a carboxylate ion are preferred. In formula (RI-III), R 31 、R 32 、R 33Represents an aryl, alkyl, alkenyl, or alkynyl group having 20 or fewer carbon atoms that can each independently have 1 to 6 substituents. From the perspectives of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, a thioaryl group having 1 to 12 carbon atoms. Z 31 - Represents a monovalent anion, which is a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion. From the perspectives of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.

[0630] As specific examples, the following examples can be cited.

[0631] [Chemical formula 36]

[0632]

[0633] [Chemical formula 37]

[0634]

[0635] [Chemical formula 38]

[0636]

[0637] [Chemical formula 39]

[0638]

[0639] When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 2 to 15% by mass relative to the total solid content of the photocurable resin composition of the present invention. The photoacid generator can contain only one type or two or more types. When two or more photoacid generators are contained, it is preferred that their total is within the above range.

[0640] <Photo-base generator>

[0641] The photocurable resin composition of the present invention can contain a photo-base generator as the photosensitive compound A.

[0642] It can also be set in the following manner: by containing a photo-base generator and a crosslinking agent described later in the photocurable resin composition, for example, the crosslinking reaction of the crosslinking agent is promoted by the base generated in the exposed area, and the exposed area is less likely to be removed by the developer than the unexposed area. According to this method, a negative relief pattern can be obtained.

[0643] As the photo-base generator, as long as it generates a base upon exposure, there is no particular limitation, and known substances can be used.

[0644] For example, as described in M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuraoka, 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), examples include transition metal compound complexes, substances having a structure such as an ammonium salt, ionic compounds in which basic components such as substances in which the amidine moiety is potentialized by forming a salt with a carboxylic acid are neutralized by forming a salt, urethane derivatives, oxime ester derivatives, non-ionic compounds in which basic components such as acyl compounds are potentialized by a urethane bond or an oxime bond, etc.

[0645] In the present invention, as the photo-base generator, urethane derivatives, amide derivatives, imide derivatives, α-cobalt complex compounds, imidazole derivatives, cinnamide derivatives, oxime derivatives, etc. are more preferred examples.

[0646] The basic substance generated from the photo-base generator is not particularly limited, and examples include compounds having an amino group, especially polyamines such as monoamines and diamines, and amidines.

[0647] As the photo-base generator, a photo-base generator preferably having no salt in its structure is preferred, and preferably there is no charge on the nitrogen atom of the base moiety generated in the photo-base generator. As the photo-base generator, it is preferred that the generated base is latentized by a covalent bond, and the mechanism for generating the base is preferably a mechanism in which the covalent bond between the nitrogen atom of the generated base moiety and an adjacent atom is cleaved to generate the base. If it is a photo-base generator having no salt in its structure, the photo-base generator can be made neutral, so the solvent solubility is better and the shelf life is extended. For this reason, the amine generated from the photo-base generator used in the present invention is preferably a primary amine or a secondary amine.

[0648] Furthermore, for the above reasons, as the photo-base generator, as described above, it is preferred that the generated base is latentized by a covalent bond, and it is preferred that the generated base is latentized by an amide bond, a urethane bond, or an oxime bond.

[0649] As the photo-base generator of the present invention, for example, photo-base generators having a cinnamide structure disclosed in Japanese Patent Application Laid-Open No. 2009-080452 and International Publication No. 2009 / 123122, photo-base generators having a urethane structure disclosed in Japanese Patent Application Laid-Open No. 2006-189591 and Japanese Patent Application Laid-Open No. 2008-247747, photo-base generators having an oxime structure or a carbamoyl oxime structure disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581, etc. can be mentioned, but it is not limited to these, and in addition, structures of known photo-base generators can be used.

[0650] In addition, as the photo-base generator, compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese Patent Application Laid-Open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010 / 064631 can be cited as examples.

[0651] In addition, as the photo-base generator, commercially available products can be used. As commercially available products, 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 Wako Pure Chemical Corporation), etc. can be mentioned.

[0652] When a photo-base generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 2 to 15% by mass, based on the total solid content of the photocurable resin composition of the present invention. The photo-base generator may contain only one kind or two or more kinds. When two or more photo-base generators are contained, it is preferable that the total is within the above range.

[0653] <Photosensitive Compound B>

[0654] In the first mode of the method for manufacturing the cured film of the present invention, the photocurable resin composition contains a compound that is not sensitive to the exposure wavelength in the first exposure step and is sensitive to the exposure wavelength in the second exposure step, that is, photosensitive compound B.

[0655] The case where photosensitive compound B is not sensitive to the exposure wavelength in the first exposure step and the case where it is sensitive to the exposure wavelength in the second exposure step can be determined by the same method as the determination method of whether it has sensitivity described in the description of photosensitive compound A above.

[0656] In the first mode, as photosensitive compound B, the following compounds can be mentioned: the same photoinitiators, photoacid generators, and photo-base generators as photosensitive compound A, and the exposure wavelength having sensitivity is different from the compound selected as photosensitive compound A.

[0657] As an example, when a photo radical polymerization initiator having sensitivity around 365 nm is used as photosensitive compound A, a photoacid generator having sensitivity around 216 nm can be used as photosensitive compound B.

[0658] And, as another example, when a photo radical polymerization initiator having sensitivity around 365 nm is used as photosensitive compound A, a photo radical polymerization initiator having sensitivity around 270 nm can also be used as photosensitive compound B.

[0659] In the second mode of the method for manufacturing the cured film 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.

[0660] The maximum absorption wavelength of photosensitive compound B is preferably 190 to 450 nm, more preferably 190 to 315 nm.

[0661] The maximum absorption wavelength of photosensitive compound B can be measured by the above method.

[0662] In the second mode, as the photosensitive compound B, examples of the compound include the same photoinitiator, photoacid generator, and photobase generator as the above-mentioned photosensitive compound A, and a compound having a maximum absorption wavelength that is 80 nm or more away from the compound selected as the photosensitive compound A.

[0663] As an example, when a photo radical polymerization initiator having a maximum absorption wavelength near 365 nm is used as the photosensitive compound A, a photoacid generator having a maximum absorption wavelength near 216 nm can be used as the photosensitive compound B.

[0664] Also, as another example, when a photo radical polymerization initiator having a maximum absorption wavelength near 365 nm is used as the photosensitive compound A, a photo radical polymerization initiator having a maximum absorption wavelength near 270 nm can also be used as the photosensitive compound B.

[0665] When a photoinitiator, photoacid generator, or photobase generator is used as the photosensitive compound B, the preferred content of these compounds is the same as the preferred content of these compounds when used as the photosensitive compound A.

[0666] In addition, regarding the preferred combinations of the photosensitive compound A and the photosensitive compound B, as described in the above modes 1 to 7.

[0667] The photosensitive compound B is preferably a compound that generates an acid through the above-mentioned second exposure step. Examples of the compound that generates an acid through the above-mentioned second exposure step include the above-mentioned photoacid generator.

[0668] When the photosensitive compound B is a compound that generates an acid through the above-mentioned second exposure step, the photocurable resin composition of the present invention preferably contains other crosslinking agents described later.

[0669] The photosensitive compound B is preferably a compound that generates radicals through the above-mentioned second exposure step. Examples of the compound that generates radicals through the above-mentioned second exposure step include the above-mentioned photo radical polymerization initiator.

[0670] When the photosensitive compound B is a compound that generates radicals through the above-mentioned second exposure step, the photocurable resin composition of the present invention preferably contains a radical crosslinking agent described later.

[0671] The photosensitive compound B is preferably a compound that generates a base through the above-mentioned second exposure step. Examples of the compound that generates a base through the above-mentioned second exposure step include the above-mentioned photobase generator.

[0672] When the photosensitive compound B is a compound that generates a base through the above-mentioned second exposure step, the photocurable resin composition of the present invention preferably contains other crosslinking agents described later, and more preferably contains an epoxy compound described later.

[0673] <Solvent>

[0674] The photocurable resin composition of the present invention preferably contains a solvent.

[0675] Any known solvent can be arbitrarily used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, and alcohols.

[0676] Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetic acid alkyl esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkoxypropionic acid alkyl esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate (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, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. as preferred esters.

[0677] Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. as preferred ethers.

[0678] Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, dihydrolevoglucosanone, etc. as preferred ketones.

[0679] As cyclic hydrocarbons, for example, preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, anisole, etc., and cyclic terpenes such as limonene.

[0680] As sulfoxides, for example, as preferred sulfoxides, dimethyl sulfoxide can be cited.

[0681] As amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0682] As ureas, preferred ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0683] As alcohols, 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, diacetone alcohol, etc. can be cited.

[0684] Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., a method of mixing two or more kinds is also preferred.

[0685] In the present invention, it is preferably one solvent 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 mixed solvent composed of two or more kinds. Particularly preferably, dimethyl sulfoxide and γ-butyrolactone are used simultaneously. Also, combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone are preferred.

[0686] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid content concentration of the photocurable resin composition of the present invention becomes 5 to 80% by mass, more preferably an amount that becomes 5 to 75% by mass, still more preferably an amount that becomes 10 to 70% by mass, still more preferably an amount that becomes 20 to 70% by mass, and even more preferably an amount that becomes 40 to 70%. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

[0687] The solvent may contain only one kind or may contain two or more kinds. When two or more kinds of solvents are contained, it is preferable that their total is within the above range.

[0688] <Crosslinking agent>

[0689] The photocurable resin composition of the present invention preferably contains a crosslinking agent.

[0690] The crosslinking agent is preferably a crosslinking agent having a group that promotes a bonding reaction with other groups by the photosensitization of the photosensitive compound B in the second exposure step under the above condition 2.

[0691] Examples of the crosslinking agent include a radical crosslinking agent or other crosslinking agents.

[0692] <Radical crosslinking agent>

[0693] The photocurable resin composition of the present invention preferably further contains a radical crosslinking agent.

[0694] The radical crosslinking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing the above ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as vinyl, allyl, vinylphenyl, and (meth)acryloyl.

[0695] Among these, as the group containing the above ethylenically unsaturated bond, (meth)acryloyl is preferable, and from the viewpoint of reactivity, (meth)acryloyloxy is more preferable.

[0696] The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds.

[0697] The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bond.

[0698] Further, from the viewpoint of the film strength of the obtained cured film, the photocurable resin composition of the present invention preferably contains three or more compounds having ethylenically unsaturated bonds as free radical crosslinking agents. As the compound having three or more of the above-described ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferred, a compound having 3 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenically unsaturated bonds is further preferred.

[0699] Further, the compound having three or more of the above-described ethylenically unsaturated bonds is preferably a compound having three or more groups containing the above-described ethylenically unsaturated bonds, more preferably a compound having 3 to 15, further preferably a compound having 3 to 10, and particularly preferably a compound having 3 to 6.

[0700] Further, from the viewpoint of the film strength of the obtained cured film, the photocurable resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-described ethylenically unsaturated bonds.

[0701] On the other hand, from the viewpoint of developability, the free radical crosslinking agent is particularly preferably a compound having two of the above-described ethylenically unsaturated bonds.

[0702] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0703] Specific examples of the free radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, and esters of unsaturated carboxylic acids with polyol compounds and amides of unsaturated carboxylic acids with polyamine compounds are preferred. Further, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanate compounds or epoxy compounds, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Further, as another example, instead of the above-described unsaturated carboxylic acids, a group of compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. can be used. As specific examples, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, and these contents are incorporated into the present specification.

[0704] Further, the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyalkylene 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 tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols such as glycerol or trimethylolethane and then subjecting them to (meth)acrylation, (meth)acrylate carbamates described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 50-006034, and Japanese Unexamined Patent Application Publication No. Sho 51-037193, polyester acrylates described in Japanese Unexamined Patent Application Publication No. Sho 48-064183, Japanese Patent Publication No. Sho 49-043191, and Japanese Patent Publication No. Sho 52-030490, epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and other polyfunctional acrylates or methacrylates; and mixtures thereof. Further, the compound described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Application Publication No. 2008-292970 is also preferably used. Further, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

[0705] Further, as other preferred radical crosslinking agents, compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond or cardo resins described in Japanese Unexamined Patent Application Publication No. 2010-160418, Japanese Unexamined Patent Application Publication No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used.

[0706] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. Sho 46-043946, Japanese Patent Publication No. Hei 01-040337, and Japanese Patent Publication No. Hei 01-040336, vinylphosphonic acid-based compounds described in Japanese Unexamined Patent Application Publication No. Hei 02-025493, etc. can also be mentioned. Further, compounds containing a perfluoroalkyl group described in Japanese Unexamined Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, the compounds introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

[0707] In addition to the above, it is also possible to preferably use the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219, and these are incorporated into this specification.

[0708] Moreover, the following compounds (obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting it to (meth)acrylation) described in Japanese Patent Application Laid-Open No. 10-062986 together with formula (1) and formula (2) and their specific examples can also be used as a radical crosslinking agent.

[0709] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as a radical crosslinking agent, and these are incorporated into this specification.

[0710] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which the (meth)acryloyl groups thereof are bonded via an ethylene glycol residue or a propylene glycol residue are preferred. The oligomer types thereof can also be used.

[0711] Examples of commercially available products as free radical crosslinking agents include 4-functional acrylate SR-494 having 4 ethyleneoxy chains manufactured by Sartomer Company, Inc., 2-functional methyl acrylate SR-209, 231, 239 having 4 vinyloxy chains manufactured by Sartomer Company, Inc., 6-functional acrylate DPCA-60 having 6 pentaoxy chains manufactured by Nippon Kayaku Co., Ltd., 3-functional acrylate TPA-330 having 3 isobutoxy chains, urethane oligomers UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0712] As the free radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Laid-Open No. Sho 51-037193, Japanese Patent Publication No. Hei 02-032293, Japanese Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Hei 62-039417, Japanese Patent Publication No. Hei 62-039418 are also preferred. Further, as the free radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Laid-Open No. Sho 63-277653, Japanese Patent Laid-Open No. Sho 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 can also be used.

[0713] The radical crosslinking agent may be a radical crosslinking agent having acid groups such as carboxyl groups and phosphoric acid groups. Among the radical crosslinking agents having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and radical crosslinking agents having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Among the radical crosslinking agents having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol are particularly preferred. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited.

[0714] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. As long as the acid value of the radical crosslinking agent is within the above range, the operability in production is excellent, and furthermore, the developability is excellent. Also, the polymerizability is good. On the other hand, from the viewpoint of the development rate during alkali development, the preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0715] From the viewpoints of pattern resolution and film stretchability, the photocurable resin composition of the present invention preferably uses bifunctional methacrylate or acrylate.

[0716] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene glycol diacrylate and the molecular weight of the polyethylene glycol chain is about 200), 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, 1,6-hexanediol dimethacrylate, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, modified dimethacrylate of isocyanuric acid, other bifunctional acrylates having a urethane bond, bifunctional methacrylates having a urethane bond can be used. Two or more of these can be used in combination as needed.

[0717] From the viewpoint of suppressing warpage caused by controlling the elastic modulus of the cured film, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether, etc. can be preferably used. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100 °C or higher under normal pressure is also preferred.

[0718] In addition, as the radical crosslinking agent having two or more functional groups, allyl compounds such as diallyl phthalate and triallyl trimers can also be used.

[0719] When the radical crosslinking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the photocurable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0720] The free radical crosslinking agent can be used alone or in combination of two or more. When two or more are used simultaneously, it is preferred that their total amount is within the above range.

[0721] <Other crosslinking agents>

[0722] The photocurable resin composition of the present invention preferably contains other crosslinking agents different from the above free radical crosslinking agents.

[0723] In the present invention, other crosslinking agents refer to crosslinking agents other than the above free radical crosslinking agents, and are preferably compounds having a plurality of groups in the molecule that promote (the formation of covalent bonds between other compounds or their reaction products in the composition) the reaction by the photosensitivity of the above photosensitive compound A or photosensitive compound B, and are preferably compounds having a plurality of groups in the molecule that promote (the formation of covalent bonds between other compounds or their reaction products in the composition) the reaction by the action of an acid or a base.

[0724] The above acid or base is an acid or a base generated from the photosensitive compound A or photosensitive compound B, that is, a photoacid generator or a photobase generator, in the first exposure step or the second exposure step.

[0725] As other crosslinking agents, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0726] As other crosslinking agents, the following compounds can be cited: for example, compounds having a structure in which an amino group-containing compound such as melamine, acetylene urea, urea, alkylene urea, or benzoguanamine reacts with formaldehyde or formaldehyde reacts with an alcohol and the hydrogen atom of the above amino group is replaced with hydroxymethyl or alkoxymethyl. The production method of these compounds is not particularly limited as long as it is a compound having the same structure as the compound produced by the above method. And it can also be an oligomer formed by self-condensation of hydroxymethyl groups of these compounds.

[0727] As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea, or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.

[0728] Among these, the photocurable resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0729] As specific examples of the melamine-based crosslinking agent, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, etc. can be cited.

[0730] As specific examples of the urea-based crosslinking agent, for example, acetylurea-based crosslinking agents such as monohydroxymethylated acetylurea, dihydroxymethylated acetylurea, trihydroxymethylated acetylurea, tetrahydroxymethylated acetylurea, monomethoxymethylated acetylurea, dimethoxymethylated acetylurea, trimethoxymethylated acetylurea, tetramethoxymethylated acetylurea, monomethoxymethylated acetylurea, dimethoxymethylated acetylurea, trimethoxymethylated acetylurea, tetraethoxymethylated acetylurea, monopropoxymethylated acetylurea, dipropoxymethylated acetylurea, tripropoxymethylated acetylurea, tetrapropoxymethylated acetylurea, monobutoxymethylated acetylurea, dibutoxymethylated acetylurea, tributoxymethylated acetylurea or tetrabutoxymethylated acetylurea, etc.;

[0731] Urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, dibutoxymethylurea, etc.

[0732] Ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea or dibutoxymethylated ethyleneurea, etc.

[0733] Propyleneurea-based crosslinking agents such as monohydroxymethylated propyleneurea, dihydroxymethylated propyleneurea, monomethoxymethylated propyleneurea, dimethoxymethylated propyleneurea, monoethoxymethylated propyleneurea, diethoxymethylated propyleneurea, monopropoxymethylated propyleneurea, dipropoxymethylated propyleneurea, monobutoxymethylated propyleneurea or dibutoxymethylated propyleneurea, etc.

[0734] 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0735] As specific examples of the benzoguanamine-based crosslinking agent, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc. can be cited.

[0736] In addition, as the compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, a compound in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0737] As specific examples of such compounds, terephthalyl alcohol, 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, bis(methoxymethyl)benzophenone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4’,4”-ethylidynetris[2,6-bis(methoxymethyl)phenol], 5,5’-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3’,5,5’-tetrakis(methoxymethyl)-1,1’-biphenyl-4,4’-diol, etc. can be cited.

[0738] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (above, manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above are manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same hereinafter) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALACMW-100LM, NIKALAC MX-750LM (above are manufactured by SANWA CHEMICAL CO., LTD.), and the like.

[0739] Moreover, the photocurable resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as other crosslinking agents.

[0740] 〔Epoxy compound (compound having an epoxy group)〕

[0741] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction at 200°C or lower, and since no dehydration reaction due to crosslinking occurs, film shrinkage is less likely to occur. Therefore, containing an epoxy compound can effectively inhibit low-temperature curing and warping of the photocurable resin composition.

[0742] The epoxy compound preferably contains a polyoxyethylene group. Thereby, the elastic modulus is further reduced, and warping can be inhibited. The polyoxyethylene group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

[0743] Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; 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, trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (epoxypropyl) siloxane, but are not limited thereto. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, New Japan Chemical Co., Ltd.)、EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600, Serviners (registered trademark) B0134, B0177 (the above are product names, manufactured by DAICEL CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0744] [Oxetane compound (compound having an oxetanyl group)]

[0745] As the oxetane compound, compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. can be cited. As specific examples, ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or two or more of them can be mixed and used.

[0746] [Benzoxazine compound (compound having a benzoxazolyl group)]

[0747] Benzoxazine compounds do not generate degassing during curing due to the crosslinking reaction derived from the ring-opening addition reaction, and further reduce thermal shrinkage to suppress warpage generation, so they are preferred.

[0748] As preferred examples of the benzoxazine compound, B-a type benzoxazine, B-m type benzoxazine, P-d type benzoxazine, F-a type benzoxazine (the above are trade names, manufactured by Shikoku Chemicals Corporation), a benzoxazine adduct of a polyhydroxystyrene resin, and a novolak type dihydrobenzoxazine compound can be mentioned. These can be used alone, or two or more of them can be used in combination.

[0749] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass with respect to the total solid content of the photocurable resin composition of the present invention. Other crosslinking agents may contain only one kind, or may contain two or more kinds. When two or more other crosslinking agents are contained, it is preferred that their total is within the above range.

[0750] <Compounds having a sulfonamide structure, compounds having a thiourea structure>

[0751] From the viewpoint of improving the adhesion of the obtained cured film to the substrate, the photocurable resin composition of the present invention preferably further contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[0752] [Compound having a sulfonamide structure]

[0753] The sulfonamide structure is a structure represented by the following formula (S-1).

[0754] [Chemical formula 40]

[0755]

[0756] In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to other structures to form a ring structure, and * each independently represents a bonding site to other structures.

[0757] The above R is preferably the same group as R in the following formula (S-2). 2 Same group.

[0758] The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and is preferably a compound having one sulfonamide structure.

[0759] The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

[0760] [Chemical formula 41]

[0761]

[0762] In formula (S-2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 can bond to each other to form a ring structure.

[0763] R 1 , R 2 and R 3 are each independently preferably a monovalent organic group.

[0764] Examples of R 1 , R 2 and R 3 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these.

[0765] As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc.

[0766] As the above cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the above cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0767] As the above alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. Examples of the above alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc.

[0768] As the above alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferred, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferred. Examples of the above alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc.

[0769] As the above aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above aryl group may have substituents such as an alkyl group. Examples of the above aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc.

[0770] Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from heterocyclic structures such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyranyl group, a triazine ring, etc.

[0771] Among these, preferably, R 1 is an aryl group and R 2 and R 3 are each independently a hydrogen atom or an alkyl group.

[0772] Examples of the compound having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalen-1-sulfonamide, naphthalen-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

[0773] [Compound having a thiourea structure]

[0774] The thiourea structure is a structure represented by the following formula (T-1).

[0775] [Chemical formula 42]

[0776]

[0777] In formula (T-1), R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, R 4 and R 5 may bond to form a ring, R 4 may bond to other structures to which * is bonded to form a ring structure, R 5 may bond to other structures to which * is bonded to form a ring structure, and * each independently represents a bonding site to other structures.

[0778] R 4 and R 5 are each independently preferably a hydrogen atom.

[0779] Examples of R 4 and R 5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these.

[0780] As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the above-mentioned alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, 2-ethylhexyl, etc.

[0781] As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the above-mentioned cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0782] As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. Examples of the above-mentioned alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, etc.

[0783] As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferred, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferred. Examples of the above-mentioned alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, butoxysilyl, etc.

[0784] As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have substituents such as an alkyl group. Examples of the above-mentioned aryl group include phenyl, tolyl, xylyl, naphthyl, etc.

[0785] As the above-mentioned heterocyclic group, examples include groups obtained by removing one hydrogen atom from heterocyclic structures such as a triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyranyl group, triazine ring, etc.

[0786] The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

[0787] The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

[0788] [Chemical formula 43]

[0789]

[0790] In formula (T-2), R 4 ~R 7 each independently represents a hydrogen atom or a monovalent organic group, and at least two of R 4 ~R 7 may be bonded to each other to form a ring structure.

[0791] In formula (T-2), R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), and the preferred modes are also the same.

[0792] In formula (T-2), R 6 and R 7 are each independently preferably a monovalent organic group.

[0793] In formula (T-2), the preferred modes of the monovalent organic groups of R 6 and R 7 are the same as the preferred modes of the monovalent organic groups of R 4 and R 5 in formula (T-1).

[0794] Examples of the compound having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylene thiourea (2-imidazolinethione), carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

[0795] 〔Content〕

[0796] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the photocurable resin composition of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.2 to 3% by mass.

[0797] The photocurable resin composition of the present invention may contain only one compound selected from the group consisting of the compound having a sulfonamide structure and the compound having a thiourea structure, or may contain two or more. When only one is contained, the content of the compound is preferably within the above range, and when two or more are contained, the total amount thereof is preferably within the above range.

[0798] <Migration inhibitor>

[0799] The photocurable resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, the transfer of metal ions from the metal layer (metal wiring) into the photocurable layer can be effectively inhibited.

[0800] As a migration inhibitor, there is no particular limitation, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having a thiourea group and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, and 4-methylbenzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

[0801] Alternatively, an ion scavenger that scavenges anions such as a halogen ion can also be used.

[0802] As other migration inhibitors, rust preventives described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used.

[0803] Specific examples of the migration inhibitor include the following compounds.

[0804] [Chemical formula 44]

[0805]

[0806] When the photocurable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass based on the total solid content of the photocurable resin composition.

[0807] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferred that their total is within the above range.

[0808] <Inhibitor>

[0809] The photocurable resin composition of the present invention preferably contains an inhibitor.

[0810] As a polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic acid, 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), aluminum N-nitroso-N-phenylhydroxylamine salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, cerium(I) N-nitrosophenylhydroxylamine salt, ammonium N-nitroso-N-(1-naphthyl)hydroxylamine, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbamate, nitrobenzene, aluminum N-nitroso-N-phenylhydroxylamine salt, ammonium N-nitroso-N-phenylhydroxylamine salt, etc. can be preferably used. Moreover, the polymerization inhibitors described in paragraph 0060 of Japanese Unexamined Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015 / 125469 can also be used.

[0811] Moreover, the following compounds (Me is methyl) can be used.

[0812] [Chemical formula 45]

[0813]

[0814] When the photocurable resin composition of the present invention contains a polymerization inhibitor, for example, the content of the polymerization inhibitor may be in the range of 0.01 to 20.0% by mass based on the total solid content of the photocurable resin composition of the present invention, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. Moreover, when the storage stability of the photocurable resin composition is required, the range of 0.02 to 15.0% by mass may also be preferably cited, and in this case, it is more preferably 0.05 to 10.0% by mass.

[0815] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, it is preferable that their total is within the above range.

[0816] <Metal adhesion improver>

[0817] The photocurable resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used for electrodes, wirings, etc. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, etc.

[0818] Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compound described in paragraph 0055 of International Publication No. 2014 / 097594. Further, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents ethyl.

[0819] [Chemical formula 46]

[0820]

[0821] As other silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride can be cited. These can be used alone or in combination of two or more.

[0822] [Aluminum-based adhesion aids]

[0823] As aluminum-based adhesion aids, for example, aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), diisopropylaluminum ethyl acetoacetate, etc. can be cited.

[0824] Moreover, as a metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used.

[0825] The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it to be above the above lower limit value, the adhesiveness between the cured film after the curing step and the metal layer becomes good, and by setting it to be below the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is preferred that their total is within the above range.

[0826] <Other additives>

[0827] Within the range where the effects of the present invention can be obtained, the photocurable resin composition of the present invention can be blended with various additives as needed. For example, sensitizers such as N-phenyldiethanolamine, surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. When blending these additives, the total blending amount is preferably set to 3% by mass or less of the solid content of the photocurable resin composition.

[0828] 〔Surfactant〕

[0829] As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0830] By containing a surfactant in the photosensitive resin composition of the present invention, the liquid characteristics (especially fluidity) during the preparation of the coating liquid can be further improved, and thereby the uniformity of the coating thickness or the liquid-saving property can be further improved. That is, when a film is formed using the 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, a film with uniform thickness and less thickness unevenness can be formed more preferably.

[0831] As fluorine-based surfactants, 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 (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. can be cited. Fluorine-based surfactants can use the compounds described in paragraphs 0015 to 0158 of Japanese Patent Laid-Open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Patent Laid-Open No. 2011-132503. As fluorine-based surfactants, block polymers can also be used. As a specific example, for example, the compounds described in Japanese Patent Laid-Open No. 2011-89090 can be cited.

[0832] Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds (including repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group)), and the following compounds can also be exemplified as fluorine-based surfactants used in the present invention.

[0833] [Chemical formula 47]

[0834]

[0835] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.

[0836] Regarding the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Laid-Open No. 2010-164965 can be cited, such as MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation.

[0837] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the coating film thickness and liquid-saving property, and also has good solubility in the composition.

[0838] Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

[0839] As hydrocarbon surfactants, for example, 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, Pionin P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL&FAT CO., LTD), etc.

[0840] As nonionic surfactants, examples include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Boyd&Moore Executive Search.), 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), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), etc.

[0841] As cationic surfactants, specifically, examples include silicone polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoeisha chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

[0842] As an anionic surfactant, specifically, examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.

[0843] The surfactant may be used alone or in combination of two or more.

[0844] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0845] 〔Sensitizer〕

[0846] The photocurable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., and causes effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids, or bases.

[0847] Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazolyl azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxacyanine-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, etc. can also be used.

[0848] For example, examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p-dimethylaminophenylvinylidene)iso-naphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethyl ethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, dibenzylacetamide, benzoylaniline, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0849] Furthermore, as the sensitizer, a sensitizing dye can also be used.

[0850] Regarding the detailed content of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of Japanese Patent Laid-Open No. 2016-027357, and this content is incorporated into the present specification.

[0851] When the photocurable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass relative to the total solid content of the photocurable resin composition of the present invention. The sensitizer can be used alone as one kind, or two or more kinds can be used simultaneously.

[0852] [Chain transfer agent]

[0853] The photocurable resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, compounds having -S-S-, -SO2-S-, -N-O-, SH, PH, SiH, and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization can be used. These generate free radicals by supplying hydrogen to low-reactivity free radicals, or can generate free radicals after oxidation and then deprotonation. In particular, thiol compounds can be preferably used.

[0854] In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used as the chain transfer agent.

[0855] When the photocurable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the photocurable resin composition of the present invention. The chain transfer agent can be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferred that their total is within the above range.

[0856] 〔Higher fatty acid derivative〕

[0857] In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanamide can be added to the photocurable resin composition of the present invention so that they are concentrated on the surface of the photocurable resin composition during the drying process after coating.

[0858] In addition, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used as the higher fatty acid derivative.

[0859] When the photocurable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photocurable resin composition of the present invention. The higher fatty acid derivative can be only one kind, or two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferred that their total is within the above range.

[0860] 〔Thermal polymerization initiator〕

[0861] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, and thus the solvent resistance can be further improved.

[0862] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

[0863] When containing a thermal polymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may contain only one kind, or may contain two or more kinds. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0864] 〔Inorganic particles〕

[0865] The resin composition of the present invention may contain inorganic fine particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0866] The average particle diameter of the above inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0867] By including a large amount of the average particle diameter of the above inorganic particles, the mechanical properties of the cured film may sometimes deteriorate. Also, if the average particle diameter of the above inorganic particles is greater than 2.0 μm, the resolution may sometimes decrease due to the scattering of exposure light.

[0868] 〔Ultraviolet absorber〕

[0869] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0870] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-butylphenyl salicylate, etc. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, etc. Further, 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-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0871] Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc. Further, examples of triazine-based ultraviolet absorbers include mono( hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc.; bis( hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, etc.; tris( hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0872] In the present invention, the above various ultraviolet absorbers may be used alone, or two or more of them may be used in combination.

[0873] The composition of the present invention may or may not contain an ultraviolet absorber. When it contains an ultraviolet absorber, the content of the ultraviolet absorber 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, based on the total solid content mass of the composition of the present invention.

[0874] [Organic titanium compound]

[0875] The resin composition of the present embodiment may contain an organic titanium compound. By containing an organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0876] Examples of the organic titanium compound that can be used include an organic titanium compound in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0877] Specific examples of the organic titanium compound are shown in the following I) to VII):

[0878] I) Titanium chelate compound: Among them, from the viewpoint of excellent storage stability of the negative photosensitive resin composition and good cured patterns, a titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are bis(triethanolamine)diisopropoxytitanium, bis(n-butoxy)bis(2,4-pentanedioate)titanium, diisopropoxybis(2,4-pentanedioate)titanium, diisopropoxybis(tetramethylheptanedioate)titanium, diisopropoxybis(ethyl acetoacetate)titanium, etc.

[0879] II) Tetraalkoxytitanium compound: For example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexoxy)titanium, tetra(isobutoxy)titanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0880] III) Titanocene compound: For example, pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0881] IV) Monoalkoxytitanium compound: For example, isopropoxytitanium tris(dioctyl phosphate), isopropoxytitanium tris(dodecyl benzenesulfonate), etc.

[0882] V) Titanium oxide compounds: such as bis(pentanedioate)titanium, bis(tetramethylheptanedioate)titanium, titanium phthalocyanine oxide, etc.

[0883] VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate, etc.

[0884] VII) Titinate coupling agents: such as isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0885] Among them, as the organotitanium compound, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred. In particular, diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0886] When the organotitanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability of the composition is excellent.

[0887] 〔Antioxidant〕

[0888] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the extensibility of the cured film and the adhesion to a metal material can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. A compound having a substituent at a position (ortho position) adjacent to the phenolic hydroxyl group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Also, regarding the antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferred. Also, a phosphorus-based antioxidant can be preferably used as the antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenz[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available products of the antioxidant include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION), etc. Also, the compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can be used as the antioxidant. Also, the composition of the present invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include a compound in which a site that functions as an antioxidant is protected by a protecting group, and in this compound, the protecting group is removed by heating at 100 to 250 °C or heating at 80 to 200 °C in the presence of an acid / base catalyst, thereby functioning as an antioxidant. Examples of the latent antioxidant include the compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Unexamined Patent Application Publication No. 2017-008219. Examples of commercially available products of the latent antioxidant include ADEKA ARKLSGPA-5001 (manufactured by ADEKA CORPORATION), etc. Examples of a preferred antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and the compound represented by the general formula (3).

[0889] [Chemical formula 48]

[0890]

[0891] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R 6 represents an alkylene group having 2 or more carbon atoms. R 7 represents an alkylene group having 2 or more carbon atoms or a 1- to 4-valent organic group containing at least 1 selected from among an O atom and an N atom. k represents an integer of 1 to 4.

[0892] The compound represented by general formula (3) inhibits the oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the resin. Also, by the rust-preventive action on the metal material, metal oxidation can be inhibited.

[0893] In order to be able to act on both the resin and the metal material simultaneously, k is more preferably an integer of 2 to 4. As R 7 , examples include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, etc., and may further have substituents. Among them, from the viewpoints of solubility in the developer and metal adhesion, an alkyl ether and -NH- are preferred, and from the viewpoints of interaction with the resin and metal adhesion based on metal complex formation, -NH- is more preferred.

[0894] Examples of the compound represented by the following general formula (3) include the following compounds, but are not limited to the following structures.

[0895] [Chemical formula 49]

[0896]

[0897] [Chemical formula 50]

[0898]

[0899] [Chemical formula 51]

[0900]

[0901] [Chemical formula 52]

[0902]

[0903] The addition amount of the antioxidant relative to the resin is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. When the addition amount is less than 0.1 part by mass, it is difficult to obtain the extended characteristics of reliability and the effect of improving the adhesion to the metal material. Moreover, when it is more than 10 parts by mass, the sensitivity of the resin composition may decrease due to the interaction with the photosensitizer. The antioxidant may be used alone or in combination of two or more. When two or more are used, it is preferred that the total amount thereof is within the above range.

[0904] <Regarding the limitation of other contained substances>

[0905] From the viewpoint of the coating surface properties, the water 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 further preferably less than 0.6% by mass.

[0906] From the viewpoint of insulation, the metal content of the photocurable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. When multiple metals are included, it is preferred that the total of these metals is within the above range.

[0907] Moreover, as a method for reducing metal impurities accidentally contained in the photocurable resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as the raw materials constituting the photocurable resin composition of the present invention, filtering the raw materials constituting the photocurable resin composition of the present invention through a filter, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.

[0908] Considering the use as a semiconductor material and from the viewpoint of wiring corrosiveness, in the photocurable resin composition of the present invention, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, when present in the state of halogen ions, it is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferred that the total of the chlorine atom and the bromine atom or the chloride ion and the bromine ion is within the above range respectively.

[0909] As a storage container for the photocurable resin composition of the present invention, conventionally known storage containers can be used. Further, as the storage container, in order to suppress the inclusion of impurities in the raw materials or the photocurable resin composition, a multilayer bottle having an inner wall of the container formed of six types of six layers of resin or a bottle having a seven-layer structure formed of six types of resin is preferably used. As such a container, for example, the container described in JP-A-2015-123351 can be cited.

[0910] <Use of the photocurable resin composition>

[0911] The photocurable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.

[0912] Further, it can also be used for forming an insulating film of a semiconductor device or forming a stress buffer film, etc.

[0913] <Preparation of the photocurable resin composition>

[0914] The photocurable resin composition of the present invention can be prepared by mixing the above-described respective components. The mixing method is not particularly limited, and it can be carried out by a conventionally known method.

[0915] Further, in order to remove foreign matters such as dust or fine particles in the photocurable resin composition, filtration using a filter is preferably carried out. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. As the filter, a filter that has been previously washed with an organic solvent can be used. In the filter filtration step, a plurality of filters can be used in parallel or in series. When using a plurality of filters, filters having different pore diameters or materials can be used in combination. Further, various materials can be filtered a plurality of times. When filtering a plurality of times, it can be a circulating filtration. Further, filtration can be carried out after pressurization. When filtration is carried out after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and still more preferably 0.05 MPa or more and 0.7 MPa or less.

[0916] In addition to filtration using a filter, impurity removal treatment using an adsorbent material can also be carried out. The filter filtration and the impurity removal treatment using an adsorbent material can also be combined. As the adsorbent material, a known adsorbent material can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be cited.

[0917] Examples

[0918] Hereinafter, examples are given to further illustrate the present invention in detail. The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0919] <Synthesis Example 1>

[0920] 〔Synthesis of Polyimide PI-1〕

[0921] Under a dry nitrogen stream, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (32.78 g (0.0895 mol)) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (1.24 g (0.005 mol)) were dissolved in N-methyl-2-pyrrolidone (NMP, 100 g) as a solution.

[0922] Bis(3,4-dicarboxyphenyl)ether dianhydride (31.02 g (0.10 mol)) was added to the above solution together with NMP (30 g), and the mixture was stirred at 20°C for 1 hour, and then stirred at 50°C for 4 hours. 3-Aminophenol (1.09 g (0.01 mol)) was added to the stirred solution, and after stirring at 50°C for 2 hours, it was stirred at 180°C for 5 hours to obtain a resin solution. Then, the resin solution was poured into water (3 L) to form a white precipitate. The white precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours. As a result, a powder of alkali-soluble polyimide (polyimide PI-1) was obtained.

[0923] <Synthesis Example 2>

[0924] 〔Synthesis of Polyimide PI-2〕

[0925] 4,4'-(Hexafluoroisopropylidene)bis(phthalic anhydride) (2.370 kg, 5.33 mol) was poured into a solution of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bis-aniline (DAPI)) (1.465 kg, 5.51 mol) in NMP (9.86 kg) at 25°C. The temperature of the reaction mixture was raised to 40°C and allowed to react for 6 hours. Then, acetic anhydride (1.125 kg) and pyridine (0.219 kg) were added, and the temperature of the reaction mixture was raised to 100°C and allowed to react for 12 hours.

[0926] The above reaction mixture was cooled to room temperature and transferred to a larger container equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate and washed with water for 1 hour (the first time). After stopping the stirring, the mixture was allowed to stand. After phase separation occurred, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed with water twice (the second and third times). The amounts of the organic solvents (ethyl acetate and acetone) and water used in the above first to third washings are shown in Table 1.

[0927] [Table 1]

[0928] The first time The second time The third time Ethyl acetate (kg) 20.5 4.1 4.1 Acetone (kg) - 2.3 2.3 Water (kg) 22.0 26.0 26.0

[0929] GBL (γ-butyrolactone, 10 kg) was added to the washed organic phase, and the solution was concentrated by distillation under reduced pressure to obtain a polymer solution. The above polymer solution was dried with a vacuum dryer to obtain polyimide (polyimide PI-2).

[0930] <Synthesis Example 3>

[0931] [Synthesis of Polyimide PI-3]

[0932] 123 ml of N-methylpyrrolidone and 54.97 g (0.124 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., product number: H1438) were added to a three-necked flask. While dissolving at 40 °C and stirring under a nitrogen stream, while maintaining the temperature inside the system at 40 °C, an 84.0 ml solution of 8.13 g (0.049 mol) of 2,3,5,6-tetramethylphenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., product number: T1457), 19.85 g (0.062 mol) of 2,2'-bis(trifluoromethyl)benzidine, and 1.971 g (0.013 mol) of 3,5-diaminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product number: D0294) in N-methylpyrrolidone was added dropwise over 30 minutes. After stirring the reaction solution at 40 °C for 2.5 hours, 2.94 g (0.037 mol) of pyridine and 31.58 g (0.31 mol) of acetic anhydride were added respectively, and then the mixture was stirred at 80 °C for 3 hours. After that, 676.6 mL of acetone was added to the reaction solution for dilution. While stirring 1.15 L of methanol and 230 mL of acetone in a stainless steel container, the acetone-diluted solution of the reaction solution was added dropwise. The obtained polymer crystals were suction filtered and dried by blowing air at 60 °C to obtain 70.9 g of a polymer.

[0933] 10 g of the above polymer and 200 ml of tetrahydrofuran were added to a three-necked flask, and while stirring at room temperature, 0.21 g (0.002 mol) of N-(2-aminoethyl)acrylamide (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added, and further stirred for 2 hours. While adding 1.5 L of ethyl acetate to a stainless steel container and stirring, a tetrahydrofuran solution of the reaction solution was added dropwise. The obtained polymer crystals were suction filtered and dried by blowing air at 60 °C, whereby 9.2 g of a polymer (polyimide PI-3) was obtained.

[0934] <Synthesis Example 4>

[0935] [Synthesis of Polyimides PI-4 and PI-5]

[0936] -Synthesis of Polyimide PI-5-

[0937] 123 ml of N-methylpyrrolidone and 54.97 g (0.124 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA, manufactured by Tokyo Chemical Industry Co., Ltd., product number: H1438) were added to a three-necked flask and dissolved at 40 °C. While stirring under a nitrogen stream and maintaining the system at 40 °C, an 84.0 ml solution of 2,3,5,6-tetramethylphenylenediamine (TeMPD, manufactured by Tokyo Chemical Industry Co., Ltd., product number: T1457) 8.13 g (0.049 mol), m-phenylenediamine (manufactured by FUJIFILM Wako Pure Chemical Corporation, product number: 164-01515) 6.69 g (0.062 mol), and 3,5-diaminobenzoic acid (DABA, manufactured by Tokyo Chemical Industry Co., Ltd., product number: D0294) 1.971 g (0.012 mol) in N-methylpyrrolidone was added dropwise over 30 minutes. After stirring the reaction solution at 40 °C for 2.5 hours, 2.94 g (0.037 mol) of pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation, product number: 166-22575) and 31.58 g (0.31 mol) of acetic anhydride (manufactured by FUJIFILM Wako Pure Chemical Corporation, product number: 018-00286) were added respectively, and the mixture was further stirred at 80 °C for 3 hours. Thereafter, 676.6 mL of acetone was added to the reaction solution for dilution. While adding 1.15 L of methanol and 230 mL of acetone to a 5 L stainless steel container and stirring, the acetone-diluted solution of the reaction solution was added dropwise. The obtained polymer crystals were subjected to suction filtration and dried by air blowing at 60 °C, whereby 60.1 g of a polymer (PI-5) was obtained.

[0938] 10 g of the above polymer, 200 ml of tetrahydrofuran, 0.00185 g (0.017 mmol) of tetramethylammonium chloride, and 0.2 g (0.002 mol) of epichlorohydrin were added to a three-necked flask. Air was introduced into the flask at 10 ml / min, and while stirring the reaction solution, the reaction solution was heated to 90 °C using an oil bath. After the temperature of the reaction solution reached 90 °C, it was further stirred for 3 hours and then cooled to room temperature. While adding 1.5 L of ethyl acetate to a stainless steel container and stirring, the tetrahydrofuran solution of the above reaction solution was added dropwise. The obtained polymer crystals were subjected to suction filtration and dried by air blowing at 60 °C, whereby 9.2 g of a polymer (polyimide PI-4) was obtained.

[0939] The structure of the polymer (PI-4) is described below. In the following formula, the subscript in parentheses represents the content ratio (molar ratio) of each repeating unit.

[0940] [Chemical formula 53]

[0941]

[0942] [Synthesis of polybenzoxazole (PBO)]

[0943] 50.0 g (0.137 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6F-BAPh) and 53.5 g (0.137 mol) of 2,2-bis(4-carboxyphenyl)hexafluoropropane (BIS-B-AF) were added to 300 g of PPA (polyphosphoric acid). After heating at 100 °C under a nitrogen stream, the temperature was raised to 200 °C at a rate of about 10 °C / min and maintained at 200 °C for 150 minutes, thereby obtaining polybenzoxazole PBO.

[0944] <Examples and Comparative Examples>

[0945] In each of the examples, the components described in Table 2 or Table 3 below were mixed respectively, thereby obtaining each photocurable resin composition. And in each of the comparative examples, the components described in Table 3 below were mixed respectively, thereby obtaining each comparative composition.

[0946] Specifically, the content of the components described in Table 2 or Table 3 was set to the amount described in "parts by mass" in Table 2 or Table 3. And in each composition, the content of the solvent was set so that the solid content concentration of the composition became the value described in Table 2 or Table 3.

[0947] The obtained photocurable resin composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter with a pore size of 0.8 μm.

[0948] And in Table 2 or Table 3, the notation "-" indicates that the composition does not contain the component.

[0949] [Table 2]

[0950]

[0951] [Table 3]

[0952]

[0953] The details of each component described in Table 2 or Table 3 are as follows.

[0954] [Resin]

[0955] · PI-1 to PI-5: PI-1 to PI-5 synthesized above

[0956] · PBO: PBO synthesized above

[0957] 〔Free radical crosslinking agent〕

[0958] · B-1: Dipentaerythritol hexaacrylate

[0959] · B-2: LIGHT ESTER TMP (manufactured by KYOEISHA CHEMICAL Co., Ltd.)

[0960] · B-3: LIGHT ESTER BP-6EM (manufactured by KYOEISHA CHEMICAL Co., Ltd.)

[0961] · B-4: LIGHT ESTER 9EG (manufactured by KYOEISHA CHEMICAL Co., Ltd.)

[0962] · B-5: LIGHT ACRYLATE DCP-A (manufactured by KYOEISHA CHEMICAL Co., Ltd.)

[0963] 〔Photosensitive compound A〕

[0964] · C-1: ADEKA NCI-930 (manufactured by ADEKA CORPORATION)

[0965] · C-2: Diazonaphthoquinone

[0966] · C-3: ADEKA NCI-831 (manufactured by ADEKA CORPORATION)

[0967] · C-4: Irgacure 784 (manufactured by BASF)

[0968] 〔Other crosslinking agents〕

[0969] · D-1: DAICEL CELLOXIDE CEL2081 (manufactured by DAICEL CORPORATION)

[0970] · D-2: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD)

[0971] · D-3: EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.)

[0972] 〔Photosensitive compound B〕

[0973] ·E-1: WPAG-145 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0974] ·E-2: Irgacure 2959 (manufactured by BASF)

[0975] ·E-3: WPBG-027 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0976] ·E-4: Irgacure 290 (manufactured by BASF)

[0977] [Silane Coupling Agent]

[0978] ·F-1: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation)

[0979] [Polymerization Inhibitor]

[0980] ·G-1: 4-Methoxy-1-naphthol

[0981] [Additive]

[0982] ·H-1: 1,3-Dibutylthiourea

[0983] [Solvent]

[0984] ·I-1: N-Methyl-2-pyrrolidone

[0985] ·I-2: Diacetone alcohol

[0986] ·I-3: Ethyl lactate

[0987] In Table 2 or Table 3, the description in the column of "Ratio in Solvent" represents the content (mass %) of each solvent relative to the total mass of the solvent.

[0988] <Evaluation>

[0989] [Evaluation of Pattern Shape]

[0990] In each of the examples and comparative examples, each photocurable resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by spin coating, thereby forming a resin composition film.

[0991] In each of the examples and comparative examples, the silicon wafer coated with the obtained resin composition film was dried on a hot plate at 80 °C for 3 minutes, thereby forming a photocurable film having the thickness described in Table 2 or Table 3 on the silicon wafer.

[0992] In the examples where it is described as "1" or "2" in the "Curing Method" column of Table 2 or Table 3, using a stepper (Nikon NSR 2005i9C), with an exposure energy of 500 mJ / cm 2 , the photocurable film on the silicon wafer was exposed through i-rays (first exposure step). The exposure was performed through a mask (pattern: 1:1 line and space, line width: binary mask with the line width described in the "Pattern Size (μm)" column of Table 2 or Table 3).

[0993] In the examples where it is described as "3" in the "Curing Method" column of Table 2 or Table 3, using a high-pressure mercury lamp, through a band-pass filter MZ405 (manufactured by Asahi Spectra Co., Ltd.), with an exposure energy of 500 mJ / cm 2 , the photocurable film on the silicon wafer was exposed through h-rays (405 nm) (first exposure step). The exposure was performed through a mask (pattern: 1:1 line and space, line width: binary mask with the line width described in the "Pattern Size (μm)" column of Table 2 or Table 3).

[0994] In the examples where it is described as "4" in the "Curing Method" column of Table 2 or Table 3, using a high-pressure mercury lamp, through a band-pass filter MZ436 (manufactured by Asahi Spectra Co., Ltd.), with an exposure energy of 500 mJ / cm 2 , the photocurable film on the silicon wafer was exposed through g-rays (436 nm) (first exposure step). The exposure was performed through a mask (pattern: 1:1 line and space, line width: binary mask with the line width described in the "Pattern Size (μm)" column of Table 2 or Table 3).

[0995] And, the photosensitive compound A and polymethyl methacrylate (PMMA, weight average molecular weight: 10,000) used in each example were dissolved in methyl ethyl ketone to prepare a composition for forming a mold film. The content of the photosensitive compound in the composition for forming a mold film relative to the total mass of the photosensitive compound A and PMMA was set to 0.5 mmol / g. And, the usage amount of methyl ethyl ketone in the composition for forming a mold film relative to the total mass of the photosensitive compound A and PMMA was appropriately set according to the film thickness of the mold film described later.

[0996] After that, by spin coating, the above composition for forming a mold film was coated on glass and dried at 80 °C for 1 minute to obtain a mold film. The film thickness of the mold film was set to 10 μm.

[0997] After that, using the above stepper, the mold film was exposed with the same exposure wavelength and exposure amount as the above exposure, and the residual rate of the photosensitive compound A was measured by the above method respectively.

[0998] Also, in the production of the above-mentioned mold film, the photosensitive compound A was replaced with the photosensitive compound B, and except for this, the residual rate of the photosensitive compound B was measured by the same method as the residual rate of the photosensitive compound A.

[0999] In each of the examples, the residual rate of the photosensitive compound A was less than 80%.

[1000] Also, in each of the examples, the residual rate of the photosensitive compound B was 80% or more.

[1001] After the above exposure, in the examples where it is recorded as "1" in the "developer" column of Table 2 or Table 3, development was carried out for 60 seconds with a 2.5 mass% aqueous solution of tetramethylammonium hydroxide, and rinsing was carried out with pure water for 20 seconds, whereby the line-and-space pattern of the exposed photocurable film was obtained.

[1002] In the examples where it is recorded as "2" in the "developer" column of Table 2 or Table 3, development was carried out for 60 seconds with cyclopentanone, and rinsing was carried out with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds, whereby the line-and-space pattern of the photocurable film was obtained.

[1003] In the examples where it is recorded as "3" in the "developer" column of Table 2 or Table 3, development was carried out for 60 seconds with a 7.5 mass% aqueous solution of tetramethylammonium hydroxide, and rinsing was carried out with pure water for 20 seconds, whereby the line-and-space pattern of the exposed photocurable film was obtained.

[1004] In the examples where it is recorded as "1" or "3" in the "curing method" column of Table 2 or Table 3, using a high-pressure mercury lamp, under the condition of 60 °C, with an exposure amount of 10 J / cm 2 the above-developed pattern was exposed (second exposure step) and cured, whereby a silicon wafer with a cured film formed thereon was obtained.

[1005] In the examples where it is recorded as "4" in the "curing method" column of Table 2 or Table 3, using a stepper (Nikon NSR2005i9C), under the condition of 60 °C, with an exposure energy of 10 J / cm 2 the above-developed pattern was exposed (second exposure step) and cured by i-rays, whereby a silicon wafer with a cured film formed thereon was obtained.

[1006] In the examples where it is recorded as "2" in the "curing method" column of Table 2 or Table 3, the above-developed pattern and the silicon wafer on which the above pattern was formed were heated at a heating rate of 10 °C / minute in a nitrogen atmosphere, and after reaching 180 °C, maintained at 180 °C for 2 hours and cured, whereby a silicon wafer with a cured film formed thereon was obtained.

[1007] In the examples where “-” is described in the “curing method” column of Table 2 or Table 3, a silicon wafer having a cured film formed thereon was obtained without performing the exposure using the above-described high-pressure mercury lamp and the heating at 180° C., and this was used as the silicon wafer having the developed pattern formed thereon.

[1008] Further, in each of the examples, exposure was performed using the above-described high-pressure mercury lamp with the same exposure wavelength and exposure amount as the above-described exposure, and in addition, the residual ratio of the photosensitive compound B was measured by the same method as the measurement of the residual ratio of the photosensitive compound B described above.

[1009] In each of the examples, the residual ratio of the photosensitive compound B was less than 80%.

[1010] On the silicon wafer having the obtained cured film formed thereon, the silicon wafer was cut in a direction perpendicular to the line-and-space pattern of the cured film to expose the cross-section of the pattern. Using an optical microscope, the cross-section of the line-and-space pattern was observed at a magnification of 200 times, and the cross-sectional shape of the pattern was evaluated.

[1011] Specifically, in each of the examples and comparative examples, the cone angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured, and evaluation was performed according to the following evaluation criteria. It can be said that the cone angle did not exceed 90° and the cross-sectional shape of the pattern was not a shape that tapered in the middle. The closer the cone angle was to 90°, the more excellent the pattern shape was.

[1012] - Evaluation Criteria -

[1013] A: The cone angle was 85° or more and 90° or less.

[1014] B: The cone angle was 80° or more and less than 85°.

[1015] C: The cone angle was less than 80°, the cross-sectional shape of the pattern was an inverted cone shape forming a cone angle greater than 90°, or the cross-sectional shape of the pattern was a shape that tapered in the middle.

[1016] 〔Elongation at Break Evaluation〕

[1017] In each of the examples and comparative examples, each photocurable resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by a spin coating method, whereby a resin composition film was formed.

[1018] In each of the examples and comparative examples, the silicon wafer having the obtained resin composition film applied thereon was dried on a hot plate at 80° C. for 3 minutes, whereby a photocurable film having the thickness described in Table 2 or Table 3 was formed on the silicon wafer.

[1019] In the examples where it is recorded as "1" or "2" in the "Curing Method" column of Table 2 or Table 3, using a stepper (Nikon NSR 2005i9C), with an exposure energy of 500 mJ / cm 2 , the photocurable film on the silicon wafer was fully exposed (first exposure step).

[1020] In the examples where it is recorded as "3" in the "Curing Method" column of Table 2 or Table 3, using a high-pressure mercury lamp, via a band-pass filter MZ405 (manufactured by Asahi Spectra Co., Ltd.), with an exposure energy of 500 mJ / cm 2 , through h-rays (405 nm), the photocurable film on the silicon wafer was fully exposed (first exposure step).

[1021] In the examples where it is recorded as "4" in the "Curing Method" column of Table 2 or Table 3, using a high-pressure mercury lamp, via a band-pass filter MZ436 (manufactured by Asahi Spectra Co., Ltd.), with an exposure energy of 500 mJ / cm 2 , through g-rays (436 nm), the photocurable film on the silicon wafer was fully exposed (first exposure step).

[1022] In the examples where it is recorded as "1" or "3" in the "Curing Method" column of Table 2 or Table 3, using a high-pressure mercury lamp, under the condition of 60 °C, with an exposure dose of 10 J / cm 2 , the above-exposed photocurable film was fully exposed (second exposure step) and cured, thereby obtaining a silicon wafer with a cured film formed thereon.

[1023] In the examples where it is recorded as "4" in the "Curing Method" column of Table 2 or Table 3, using a stepper (Nikon NSR2005i9C), under the condition of 60 °C, with an exposure energy of 10 J / cm 2 , through i-rays, the above-developed pattern was fully exposed (second exposure step) and cured, thereby obtaining a silicon wafer with a cured film formed thereon.

[1024] In the examples where it is recorded as "2" in the "Curing Method" column of Table 2 or Table 3, the above-exposed photocurable film was heated in a nitrogen atmosphere at a heating rate of 10 °C / minute. After reaching 180 °C, it was maintained at 180 °C for 2 hours and cured, thereby obtaining a silicon wafer with a cured film formed thereon.

[1025] In the examples where it is recorded as "-" in the "Curing Method" column of Table 2 or Table 3, no exposure using the above high-pressure mercury lamp and heating at 180 °C was performed, and the silicon wafer with the exposed photocurable film formed using the stepper was obtained and used as the silicon wafer with the cured film formed thereon.

[1026] After each operation, the cured film was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer. Hereinafter, the peeled cured film is also referred to as cured film 1.

[1027] Regarding the elongation at break of the above-mentioned cured film 1, using a tensile testing machine (TENSILON), the crosshead speed was set to 300 mm / minute, the specimen width was set to 10 mm, the specimen length was set to 50 mm, and for the long side direction of the film, the elongation at break was measured in an environment of 25°C and 65% relative humidity (RH) in accordance with JIS-K6251:2017. The elongation at break is represented by E b (%) = (L b - L0) / L0 × 100 (E b : elongation at break at the time of cutting, L0: length of the cured film before the test, L b : length of the cured film when the cured film is cut) was calculated. The elongation at break in the long side direction was measured 5 times, and the arithmetic mean value thereof was used as the index value. Evaluation was carried out according to the following evaluation criteria. The evaluation results are described in the "elongation at break evaluation" column of Table 2 or Table 3. It can be said that the larger the above index value, the more excellent the elongation at break of the obtained cured film, and the excellent film strength.

[1028] -Evaluation criteria-

[1029] A: The above index value exceeds 60%.

[1030] B: The above index value exceeds 40% and is 60% or less.

[1031] C: The above index value is 40% or less.

[1032] 〔Solvent resistance evaluation〕

[1033] A silicon wafer having a cured film formed thereon was obtained in the same manner as the method described in the above elongation at break evaluation.

[1034] The silicon wafer having the above-mentioned cured film formed thereon was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and then air-dried. The film thickness of the cured film before and after immersion was measured, and the solvent resistance was evaluated according to the following evaluation criteria.

[1035] The evaluation results are described in the "solvent resistance" column of Table 2 or Table 3. It can be said that the smaller the film thickness change, the more excellent the solvent resistance.

[1036] -Evaluation criteria-

[1037] A: The film thickness change (film thickness after immersion / film thickness before immersion × 100 (%)) is less than 95%.

[1038] B: The film thickness change is 95% or more and less than 80%.

[1039] C: The film thickness change is 80% or more.

[1040] <Example 17>

[1041] The solid component concentration was adjusted to 30% by mass using the composition of Example 1, the coating method was changed from spin coating to slit coating, the coating GAP was set to 100 μm, and the slit die scanning speed was set to 5 mm / second for coating. Other evaluations were performed in the same manner as in Example 1, and the evaluation results were also the same as in Example 1.

[1042] <Example 18>

[1043] The solid component concentration was adjusted to 30% by mass using the composition of Example 2, the coating method was changed from spin coating to slit coating, the coating GAP was set to 100 μm, and the slit die scanning speed was set to 5 mm / second for coating. Other evaluations were performed in the same manner as in Example 2, and the evaluation results were also the same as in Example 2.

[1044] From the above results, it can be seen that according to the method for manufacturing a cured film of the present invention, compared with Comparative Examples 1 to 3, a cured film having excellent pattern shape and film strength can be obtained. The method for manufacturing the cured film includes: a first exposure step of exposing a part of a photocurable film formed of a photocurable resin composition; a development step of developing the exposed photocurable film with a developer to obtain a pattern; and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step. The photocurable resin composition includes: at least one resin selected from the group consisting of polyimide and polybenzoxazole; a photosensitive compound A sensitive to the exposure wavelength in the first exposure step; and a photosensitive compound B not sensitive to the exposure wavelength in the first exposure step but sensitive to the exposure wavelength in the second exposure step. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step, and the manufacturing method satisfies at least one of the above Conditions 1 and 2.

[1045] Moreover, it is known that, according to the method for manufacturing a cured film of the present invention, a cured film excellent in pattern shape and film strength can be obtained as compared with Comparative Examples 1 to 3. The method for manufacturing the cured film includes: a first exposure step of exposing a part of a photocurable film formed of a photocurable resin composition; a development step of developing the exposed photocurable film with a developer to obtain a pattern; and a second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step. The photocurable resin composition includes: at least one resin selected from the group including polyimide and polybenzoxazole; a photosensitive compound A having a difference in maximum absorption wavelength of 80 nm or more; and a photosensitive compound B. The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step. The manufacturing method satisfies at least one of the above Conditions 1 and 2.

[1046] In the method for manufacturing a cured film of Comparative Example 1 or Comparative Example 3, curing based on heating was performed instead of the second exposure step. In these examples, a poor pattern shape was found.

[1047] In the method for manufacturing a cured film of Comparative Example 2, curing equivalent to the second exposure step was not performed. In these examples, a poor elongation at break (film strength) of the cured film was found.

[1048] <Example 101>

[1049] By spin coating, the photocurable resin composition used in Example 1 was applied in a layer on the surface of a copper thin layer of a resin substrate having a copper thin layer formed on its surface, and dried at 80°C for 5 minutes. After forming a photocurable layer with a film thickness of 30 μm, ...

Claims

1. A method for manufacturing a cured film, comprising: A first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition; A development step of developing the exposed photocurable film with a developer to obtain a pattern; And A second exposure step of exposing the pattern with light including light having a wavelength different from the wavelength of the light used in the first exposure step, The photocurable resin composition includes: At least one resin selected from the group including polyimide and polybenzoxazole; A photosensitive compound A that is sensitive to the exposure wavelength in the first exposure step; and A photosensitive compound B that is not sensitive to the exposure wavelength in the first exposure step and is sensitive to the exposure wavelength in the second exposure step; The photosensitive compound A is a compound that changes the solubility of the photocurable film in the developer in the first exposure step, The manufacturing method satisfies at least one of the following Condition 1 and Condition 2: Condition 1: The resin in the photocurable resin composition includes a group whose bonding reaction with other groups is promoted by the photosensitization of the photosensitive compound B in the second exposure step; Condition 2: The photocurable resin composition further includes a crosslinking agent having a group whose bonding reaction with other groups is promoted by the photosensitization of the photosensitive compound B in the second exposure step.

2. The method for manufacturing a cured film according to claim 1, wherein The photosensitive compound A is a compound that generates free radicals through the first exposure step.

3. The method for manufacturing a cured film according to claim 1 or 2, wherein The photosensitive compound B is a compound that generates an acid through the second exposure step.

4. The method for manufacturing a cured film according to claim 1 or 2, wherein The photosensitive compound B is a compound that generates free radicals through the second exposure step.

5. The method for manufacturing a cured film according to claim 1 or 2, wherein The photosensitive compound B is a compound that generates a base through the second exposure step.

6. The method for manufacturing a cured film according to claim 1, wherein The photosensitive compound A is a photo radical polymerization initiator, and the photosensitive compound B is a photoacid generator.

7. The method for manufacturing a cured film according to claim 1, wherein Both the photosensitive compound A and the photosensitive compound B are photo radical polymerization initiators.

8. The method for manufacturing a cured film according to claim 1 or 2, wherein The exposure in the first exposure step is exposure based on i-ray.

9. A method for manufacturing a laminate, comprising the method for manufacturing a cured film according to any one of claims 1 to 8.

10. A method for manufacturing an electronic device, comprising the method for manufacturing a cured film according to any one of claims 1 to 8 or the method for manufacturing a laminate according to claim 9.

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