Method for manufacturing cured product, method for manufacturing laminate, and method for manufacturing semiconductor device

Abstract

The present application provides a method for manufacturing a cured product, a method for manufacturing a laminate including the method for manufacturing a cured product, and a method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate. The method for manufacturing a cured product, the method for manufacturing a laminate including the method for manufacturing a cured product, and the method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate include: a film forming step of forming a photosensitive film by applying a photosensitive composition on a substrate; an exposure step of selectively exposing the photosensitive film; a development step of developing the exposed photosensitive film using a developer to form a pattern; and an electromagnetic wave irradiation step of irradiating the pattern obtained by the development step with an electromagnetic wave having a wavelength of 780 nm or more and 5 μm or less.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a cured material, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device. Background Technology

[0002] Resins such as polyimide, polybenzoxazole, and polyamide-imide are suitable for a variety of applications due to their excellent heat resistance and insulation properties. While there are no particular limitations on these applications, examples include using patterns containing these resins as insulating films, sealing materials, or protective films in the context of actual semiconductor devices. Furthermore, patterns containing these resins can also be used as base films or cover films for flexible substrates.

[0003] For example, in the above-described applications, resins such as polyimide, polybenzoxazole, or polyamide-imide are used in the form of a photosensitive composition comprising a curable resin such as a polyimide precursor, a polybenzoxazole precursor, or a polyamide-imide precursor.

[0004] This photosensitive composition is applied to a substrate, for example, by coating, and then exposed, developed, modified, etc., as needed, thereby forming a cured product of polyimide precursor, polybenzoxazole precursor, polyamide-imide precursor, etc., on the substrate.

[0005] Photosensitive compositions can be applied using known coating methods, and can be developed to form fine patterns and complex shapes. Therefore, the cured products offer a high degree of design freedom and excellent manufacturing adaptability. Considering the high performance of resins such as polyimide, polybenzoxazole, and polyamide-imide, and this excellent manufacturing adaptability, there is growing anticipation for the industrial application development of manufacturing methods for cured products using photosensitive compositions containing curable resins.

[0006] For example, Patent Document 1 describes a method that includes heating polyamic acid fibers at a temperature ranging from a first temperature to a second temperature for a period of 5 seconds to 5 minutes in order to form polyimide fibers, wherein the first temperature is the imidization temperature of the polyamic acid and the second temperature is the decomposition temperature of the polyimide.

[0007] Patent Document 2 describes a resin composition comprising a polyimide precursor containing specific structural units and a solvent, wherein the solvent is a mixture of an amide solvent and a non-amide solvent with a boiling point of 160°C or higher, and contains a specific compound in an amount of more than 0 ppm and less than 1200 ppm based on the mass of the resin composition.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Publication No. 2013-539824

[0011] Patent Document 2: Japanese Patent Application Publication No. 2019-203120 Summary of the Invention

[0012] The technical problem to be solved by the invention

[0013] In conventional methods for manufacturing cured products using photosensitive compositions containing curable resins such as polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors, there is a need to improve the elongation at break of the obtained cured product and the chemical resistance of the pattern formed by the cured product.

[0014] The purpose of this invention is to provide a method for manufacturing a cured product that can obtain a cured product with excellent elongation at break and chemical resistance, a method for manufacturing a laminate including the above-mentioned method for manufacturing a cured product, and a method for manufacturing a semiconductor device including the above-mentioned method for manufacturing a cured product or the above-mentioned method for manufacturing a laminate.

[0015] means for solving technical problems

[0016] Examples of representative embodiments of the present invention are shown below.

[0017] <1> A method for manufacturing a solidified material, comprising:

[0018] The film forming process involves applying a photosensitive composition onto a substrate to form a photosensitive film;

[0019] In the exposure process, the above-mentioned photosensitive film is selectively exposed;

[0020] In the developing process, a developing solution is used to develop the exposed photosensitive film to form a pattern; and

[0021] The electromagnetic wave irradiation process involves irradiating the pattern obtained through the above-mentioned development process with electromagnetic waves of wavelengths of 780 nm or higher and 5 μm or lower.

[0022] <2> according to <1> The method for manufacturing the cured product, wherein the photosensitive composition comprises at least one resin selected from polyimide precursor, polybenzoxazole precursor, polyamide-imide precursor, epoxy resin and phenolic resin.

[0023] <3> according to <1> or <2> The method for manufacturing the cured product, wherein the photosensitive composition comprises at least one resin selected from polyimide precursor, polybenzoxazole precursor and polyamide-imide precursor.

[0024] <4> according to <1> to <3> The method for manufacturing a cured product according to any one of the above methods, wherein the photosensitive composition comprises a polymeric compound.

[0025] <5> according to <1> to <4> The method for manufacturing a cured product according to any one of the above methods, wherein the photosensitive composition comprises an organometallic complex as a polymerization initiator.

[0026] <6> according to <1> to <5> The method for manufacturing a cured product according to any one of the following methods, wherein the glass transition temperature of the obtained cured product exceeds 200°C.

[0027] <7> according to <1> to <6> In any one of the methods for manufacturing a cured product, the temperature of the pattern in the electromagnetic irradiation process is 300°C or less.

[0028] <8> according to <1> to <7> In any one of the methods for manufacturing a cured material, in the electromagnetic wave irradiation step described above, the total time for irradiating the pattern with the electromagnetic wave is 60 minutes or less.

[0029] <9> according to <1> to <8> The method for manufacturing a cured product according to any one of the above-mentioned methods, wherein the electromagnetic wave irradiation process is carried out in an inactive gas atmosphere.

[0030] <10> according to <1> to <9> The method for manufacturing a cured product according to any one of the above-mentioned methods, wherein the electromagnetic wave irradiation process is carried out in an environment with an oxygen concentration of 1000 ppm or less.

[0031] <11> according to <1> to <10> The method for manufacturing a cured product according to any one of the above-mentioned methods, wherein the thickness of the photosensitive film is 1 μm or more.

[0032] <12> according to <1> to <11> The method for manufacturing a cured product according to any one of the following methods, wherein the substrate is a substrate having metal wiring on the surface on which the photosensitive film is formed.

[0033] <13> according to <1> to <12> The method for manufacturing the cured product according to any one of the above methods, wherein the photosensitive composition comprises a photopolymerization initiator or a photoacid generator.

[0034] <14> A method for manufacturing a laminate, comprising repeating multiple times <1> to <13> The process of the method for manufacturing the cured product as described in any one of the above.

[0035] <15> according to <14> The method for manufacturing the laminate further includes a metal layer forming step, which forms a metal layer on a layer formed from the cured material during the aforementioned multiple-stage curing process.

[0036] <16> A method for manufacturing a semiconductor device, comprising: <1> to <13> The method for manufacturing the cured product as described in any one of the above statements or <14> or <15> The method for manufacturing the aforementioned laminate.

[0037] Invention Effects

[0038] According to the present invention, there is a method for manufacturing a cured product that can obtain a cured product with excellent elongation at break and chemical resistance, a method for manufacturing a laminate including the above-described method for manufacturing a cured product, and a method for manufacturing a semiconductor device including the above-described method for manufacturing a cured product or the above-described method for manufacturing a laminate. Detailed Implementation

[0039] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0040] In this specification, the numerical range indicated by the symbol “~” represents the range included by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0041] In this specification, the term "process" not only refers to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended function of the process can be achieved.

[0042] Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups (atomic groups) include both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0043] In this specification, unless otherwise stated, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0044] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either one.

[0045] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0046] In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0047] In this specification, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise stated, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. Where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise stated, detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0048] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer in the multilayer of interest. That is, a third layer or element may be further sandwiched between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Furthermore, unless otherwise stated, the direction in which the layers are gradually stacked relative to the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." In addition, this setting of up and down directions is for the convenience of explaining this specification; in practice, the "upper" direction in this specification may also be different from vertically upward.

[0049] In this specification, unless otherwise stated, each component included in the composition may also comprise two or more compounds corresponding to that component. Furthermore, unless otherwise stated,

[0050] The content of each component in the composition represents the total content of all compounds corresponding to that component.

[0051] In this specification, unless otherwise stated, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0052] In this specification, the preferred combination of methods is a more preferred method.

[0053] (Method for manufacturing solidified products)

[0054] The method for manufacturing the cured product of the present invention includes: a film forming step, wherein a photosensitive composition is applied to a substrate to form a photosensitive film; an exposure step, wherein the photosensitive film is selectively exposed; a developing step, wherein the exposed photosensitive film is developed using a developing solution to form a pattern; and an electromagnetic wave irradiation step, wherein the pattern obtained by the developing step is irradiated with an electromagnetic wave of a wavelength of 780 nm or more and 5 μm or less.

[0055] According to the method for manufacturing cured products of the present invention, cured products with excellent elongation at break and chemical resistance can be obtained.

[0056] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0057] The method for manufacturing a cured product according to the present invention includes an electromagnetic wave irradiation step, wherein the electromagnetic wave irradiation step irradiates an electromagnetic wave with a wavelength of 780 nm or more and 5 μm or less onto a pattern obtained by the above-described developing step.

[0058] The photosensitive film is heated through this electromagnetic wave irradiation process.

[0059] Regarding the heating based on the above-mentioned electromagnetic wave irradiation process, it is considered to be much faster than heating using conventional box ovens, heating plates, etc., and to be performed when the photosensitive film is nearly uniform (for example, when there is little uneven heating caused by the position of the film).

[0060] Therefore, it is speculated that, for example, the curing of the curable resin contained in the photosensitive film (e.g., cyclization of polyimide precursors, polymerization of epoxy resins, etc.) and the crosslinking of polymeric compounds proceed rapidly, and the degree of curing and crosslinking density increase, thus obtaining a cured product with excellent chemical resistance.

[0061] Furthermore, it is speculated that when the photosensitive film contains a curable resin, the degree of cyclization of the curable resin increases as described above, thus a cured product with excellent elongation at break can be obtained.

[0062] In particular, when the photosensitive film contains a curable resin and a polymeric compound, heating using conventional methods such as box ovens results in slow heating rates. Therefore, sometimes the polymeric compound is cross-linked first, followed by curing of the curable resin. In such cases, the presence of the cross-linked polymeric compound reduces the degree of freedom in structural changes of the curable resin, sometimes leading to a decrease in the degree of curing of the curable resin. In the method for manufacturing the cured product of the present invention, it is presumed that because heating via an electromagnetic wave irradiation process results in a very fast heating rate, curing of the curable resin can be performed even when the degree of cross-linking of the polymeric compound is low. Therefore, the degree of curing of the curable resin is higher, resulting in excellent elongation at break.

[0063] Patent Document 1 to Patent Document 2 do not describe a method for manufacturing a cured product that includes the aforementioned film formation process, exposure process, development process, and electromagnetic wave irradiation process.

[0064] The method for manufacturing the cured product of the present invention will be described in detail below.

[0065] <Membrane Formation Process>

[0066] The method for manufacturing the cured product of the present invention includes a film forming step of applying a photosensitive composition onto a substrate to form a photosensitive film.

[0067] Details of the photosensitive composition used in the film formation process will be described later.

[0068] [Substrate]

[0069] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates with metal layers formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0070] Furthermore, layers such as a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0071] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[0072] For the dimensions of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the shorter side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

[0073] Furthermore, as a substrate, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0074] Furthermore, when a photosensitive film is formed by applying a photosensitive composition to the surface of a resin layer (e.g., a layer formed from a cured material) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0075] Furthermore, the substrate is preferably a substrate with metal wiring on the surface on which the photosensitive film is formed.

[0076] In the above-described manner, the semiconductor substrate is preferably used as the substrate material.

[0077] Furthermore, the metal wiring described above can be exemplified by wiring based on copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing these metals, more preferably wiring based on copper, aluminum and alloys containing these metals, and even more preferably wiring based on copper or copper alloys.

[0078] Coating is preferred as a method for applying the photosensitive composition to a substrate.

[0079] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of uniformity of the photosensitive film thickness, spin coating, slot coating, spray coating, or inkjet coating are more preferred. From the viewpoints of uniformity of the photosensitive film thickness and productivity, spin coating and slot coating are preferred. By adjusting the concentration of the solid components of the photosensitive composition or the coating conditions according to the method, a photosensitive film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0080] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[0081] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can preferably be used in this invention.

[0082] Furthermore, a process can be performed to remove excess photosensitive film from the ends of the substrate. Examples of such processes include edge rinsing (EBR) and back rinsing.

[0083] Alternatively, a pre-wetting process can be used, in which various solvents are applied to the substrate to improve its wettability before the photosensitive composition is applied to the substrate.

[0084] The thickness of the photosensitive film (the film thickness after the drying process if the manufacturing method of the cured material includes the drying process described later) is not particularly limited, but it is preferably 1 μm or more, more preferably 1 to 100 μm, and even more preferably 2 to 40 μm.

[0085] If the film thickness is within the above range, the effect of suppressing uneven heating at different locations in the film during the electromagnetic wave irradiation process described later is significant, and heating can be carried out quickly.

[0086] <Drying Process>

[0087] After the film formation process (layer formation process), the above-mentioned photosensitive film can be used in the drying process (drying process) to remove the solvent.

[0088] That is, the method for manufacturing the cured product of the present invention may include a drying step, which dries the photosensitive film formed by the film forming step.

[0089] Furthermore, the aforementioned drying process is preferably performed after the film formation process and before the exposure process.

[0090] The drying temperature of the photosensitive film in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can also be performed under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0091] <Exposure Process>

[0092] The aforementioned photosensitive film is used in the exposure process of selectively exposing the photosensitive film.

[0093] That is, the method for manufacturing the cured material of the present invention includes an exposure step, which selectively exposes the photosensitive film formed by the film forming step.

[0094] Selective exposure means exposing a portion of the photosensitive film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (unexposed areas) are formed on the photosensitive film.

[0095] Regarding exposure, there are no specific requirements as long as the photosensitive film can be sensitive. For example, the preferred exposure energy, calculated based on an exposure wavelength of 365nm, is 50–10,000 mJ / cm². 2 More preferably, it is 200–8,000 mJ / cm². 2 .

[0096] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0097] Regarding the exposure wavelength, examples related to the light source include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), and wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. For the photosensitive composition, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is even more preferred. This allows for particularly high exposure sensitivity.

[0098] Furthermore, there are no particular limitations on the exposure method, as long as it is an exposure of at least a portion of the photosensitive film formed by the photosensitive composition. However, examples include exposure using a photomask and exposure based on direct laser imaging.

[0099] <Post-exposure heating process>

[0100] The aforementioned photosensitive film can be used in a process where heating is performed after exposure (post-exposure heating process).

[0101] That is, the method for manufacturing the cured material of the present invention may include a post-exposure heating step, which heats the photosensitive film that has been exposed by the exposure step.

[0102] The post-exposure heating process can be performed after the exposure process and before the development process.

[0103] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0104] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0105] Regarding the heating rate in the post-exposure heating process, the rate from the initial heating temperature to the maximum heating temperature is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0106] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0107] There are no particular limitations on the heating mechanism used in the post-exposure heating process; commonly known heating plates, ovens, infrared heaters, etc., can be used.

[0108] Furthermore, it is preferable to carry out the process in a low-oxygen atmosphere by passing inactive gases such as nitrogen, helium, or argon through the gas during heating.

[0109] <Developing Process>

[0110] The exposed photosensitive film is then used in the developing process to form a pattern by developing it with a developing solution.

[0111] That is, the method for manufacturing the cured material of the present invention includes a developing step, which uses a developing solution to develop a photosensitive film that has been exposed by an exposure step to form a pattern.

[0112] The exposed and unexposed portions of the photosensitive film are removed by developing the film, thus forming a pattern.

[0113] The development process that removes the non-exposed portion of the photosensitive film is called negative development, while the development process that removes the exposed portion of the photosensitive film is called positive development.

[0114] [Developing solution]

[0115] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0116] When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total mass of the developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0117] When the developer contains an organic solvent, esters are preferably included, 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., 3-alkyl...). Methyl oxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate) ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, 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 (PGMFA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones. Examples of suitable alternatives include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0118] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is especially preferred.

[0119] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content can be 100% by mass.

[0120] The developer may further contain other ingredients.

[0121] Other components include, for example, well-known surfactants and well-known defoamers.

[0122] [Method for supplying developer]

[0123] Regarding the method of supplying the developer, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate on which the photosensitive film is formed in the developer, using a nozzle to supply the developer to the photosensitive film formed on the substrate for water-pit development, or continuously supplying the developer. There are no particular limitations on the type of nozzle, and examples include straight nozzles, spray nozzles, and mist nozzles.

[0124] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to use a method of supplying developer with a straight nozzle or a method of continuous supply with a spray nozzle. From the viewpoint of developer penetration into the image area, it is more preferable to use a method of supplying with a spray nozzle.

[0125] Furthermore, the process can be repeated multiple times, where after continuously supplying developer using a straight nozzle, the substrate is rotated to remove developer from the substrate, and after rotation drying, the substrate is continuously supplied again using a straight nozzle to remove developer from the substrate.

[0126] Furthermore, as a method for supplying developer in the developing process, it is possible to employ a process of continuously supplying developer to the substrate, a process of keeping the developer in a substantially static state on the substrate, a process of vibrating the developer on the substrate using ultrasound or the like, and a process of combining these methods.

[0127] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution is not particularly specified, but it is preferably carried out at 10 to 45°C, more preferably at 18 to 30°C.

[0128] In the developing process, after treatment with the developer, the pattern can be further cleaned (rinsed) using the rinsing solution. Furthermore, the rinsing solution can be supplied before the developer that was in contact with the pattern has completely dried.

[0129] [Rinse solution]

[0130] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0131] When the rinsing solution contains an organic solvent, the organic solvent, preferably an ester, includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkoxypropionic acid esters). Methyl esters, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate) Ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, 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, Examples of preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; as cyclic hydrocarbons, examples of preferred examples include aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene; as sulfoxides, examples of preferred examples include dimethyl sulfoxide; as alcohols, examples of preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc.; and as amides, examples of preferred examples include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0132] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0133] When the rinsing solution contains an organic solvent, it is preferable that 50% or more by mass of the rinsing solution is an organic solvent, more preferably 70% or more by mass, and even more preferably 90% or more by mass. Furthermore, it is also permissible for the rinsing solution to contain 100% by mass of an organic solvent.

[0134] The rinsing solution may further contain other ingredients.

[0135] Other components include, for example, well-known surfactants and well-known defoamers.

[0136] [Method for supplying flushing fluid]

[0137] Regarding the method of supplying the rinsing solution, there are no particular restrictions as long as the desired pattern can be formed. Methods include immersing the substrate in the rinsing solution, developing the substrate in a water pit, supplying the rinsing solution to the substrate in the form of a spray, and continuously supplying the developing solution to the substrate through a mechanism such as a straight nozzle.

[0138] From the viewpoints of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying rinsing fluid such as spray nozzles, straight nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred, and from the viewpoint of the penetrability of the rinsing fluid to the image area, a mist nozzle is even more preferred. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[0139] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed photosensitive film through a straight nozzle, and more preferably a process of supplying rinsing liquid through a spray nozzle.

[0140] Furthermore, as a method for supplying rinsing fluid in the rinsing process, methods such as continuously supplying rinsing fluid to the substrate, keeping the rinsing fluid in a substantially static state on the substrate, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combining these methods are all possible.

[0141] The preferred rinsing time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly specified, but it is preferably performed at 10 to 45°C, more preferably at 18 to 30°C.

[0142] <Electromagnetic wave irradiation process>

[0143] The method for manufacturing a cured product according to the present invention includes an electromagnetic wave irradiation step, wherein the electromagnetic wave irradiation step irradiates an electromagnetic wave with a wavelength of 780 nm or more and 5 μm or less onto a pattern obtained by the above-described developing step.

[0144] For example, in the case where the photosensitive film contains a specific resin described later, the pattern is heated by an electromagnetic wave irradiation process to cure the specific resin.

[0145] In the electromagnetic wave irradiation process, the electromagnetic waves only need to irradiate at least a portion of the pattern obtained through the developing process, but it is preferable to irradiate the entire pattern.

[0146] There is no particular limitation on the amount of irradiation, as long as the temperature of the photosensitive film and the irradiation time of the electromagnetic waves are within the range described later.

[0147] The electromagnetic waves used in the electromagnetic wave irradiation process are electromagnetic waves with a wavelength of 780 nm or more and 5 μm or less, preferably electromagnetic waves with a wavelength of 900 nm or more and 4 μm or less, and more preferably electromagnetic waves with a wavelength of 1000 nm or more and 3.5 μm or less.

[0148] In the case where the electromagnetic waves mentioned above include electromagnetic waves with multiple wavelengths, it is sufficient as long as the wavelength of at least one electromagnetic wave is within the above range.

[0149] When the photosensitive composition contains a photopolymerization initiator, the manner in which the electromagnetic waves described above do not contain electromagnetic waves with wavelengths below 550 nm is also one of the preferred embodiments of the present invention.

[0150] Furthermore, when the photosensitive composition contains a photoalkali generating agent, the generation of alkali derived from the photoalkali generating agent is promoted. Therefore, the above-mentioned electromagnetic wave containing electromagnetic waves with wavelengths of 550 nm or less is also one of the preferred embodiments of the present invention.

[0151] Furthermore, the aforementioned electromagnetic waves, which include electromagnetic waves of various wavelengths (so-called broad electromagnetic waves), have a high tolerance for the composition of photosensitive films and are sometimes preferred.

[0152] As an exposure light source, known examples include infrared lamps, infrared diodes, and infrared irradiation devices. These can be used without particular limitations, taking into account factors such as the wavelength and energy of the irradiated electromagnetic waves. Among these, a halogen heater (halogen lamp) is preferred.

[0153] The temperature (maximum temperature) of the pattern in the electromagnetic wave irradiation process is not particularly limited, and can be determined by considering the components contained in the photosensitive film. However, it is preferred to be 400°C or below, more preferably 300°C or below, more preferably 250°C or below, and can also be set to 240°C or below.

[0154] The lower limit of the above-mentioned maximum temperature is preferably 150°C or higher, and more preferably 180°C or higher.

[0155] In the electromagnetic wave irradiation process, there is no particular limitation on the total time for irradiating the pattern with the electromagnetic waves. It can be determined by taking into account the thickness of the photosensitive film, the components contained in the photosensitive film, etc. However, it is preferable to be 60 minutes or less, and more preferably 30 minutes or less.

[0156] The electromagnetic wave irradiation process is preferably carried out in an inert gas atmosphere.

[0157] Examples of inert gases include halogen gases such as N2 and Ar.

[0158] Furthermore, the electromagnetic wave irradiation process is preferably carried out under reduced pressure or in a vacuum.

[0159] Furthermore, the electromagnetic irradiation process is preferably carried out in a reducing gas atmosphere such as H2 gas or formic acid gas.

[0160] In these methods, the electromagnetic irradiation process is preferably carried out in an environment with an oxygen concentration of 1,000 ppm or less, more preferably in an environment with an oxygen concentration of 100 ppm or less, and even more preferably in an environment with an oxygen concentration of 10 ppm or less. The lower limit of the oxygen concentration is not particularly limited, as long as it is 0 ppm or more.

[0161] Regarding the heating rate of the pattern in the electromagnetic wave irradiation process, it is preferably 5°C / min or more from the temperature at the start of the electromagnetic wave irradiation process to the aforementioned maximum temperature, more preferably 10°C / min or more, and even more preferably 100°C / min or more.

[0162] The initial temperature of the pattern at the start of the electromagnetic wave irradiation process is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial temperature at the start of the electromagnetic wave irradiation process refers to the temperature at which electromagnetic waves are first irradiated during the process. For example, if the photosensitive composition contains a solvent, it is preferable to raise the temperature from a temperature 30°C to 200°C lower than the boiling point of the solvent.

[0163] The time for maintaining the above-mentioned maximum temperature during the electromagnetic wave irradiation process is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0164] Furthermore, during the electromagnetic wave irradiation process, heating can also be achieved through other heating mechanisms.

[0165] The heating described above can be carried out simultaneously with electromagnetic wave irradiation, or it can be carried out before or after the start of electromagnetic wave irradiation.

[0166] Examples of heating mechanisms include heating plates, electric ovens, and hot air ovens.

[0167] As an electromagnetic wave irradiation mechanism in an electromagnetic wave irradiation process, it is possible to use known infrared irradiation devices such as infrared ovens without particular limitations.

[0168] The pattern can be cooled after the electromagnetic wave irradiation process is completed.

[0169] <Post-development exposure process>

[0170] The pattern obtained through the developing process (or the washed pattern in the case of a washing process) can be used not only in the electromagnetic irradiation process mentioned above, but also in the post-development exposure process of the pattern after the exposure and developing process.

[0171] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step, wherein the post-development exposure step exposes the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

[0172] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photosensitization by a photoalkali generator or the removal of acid-degrading groups by photosensitization by a photoacid generator.

[0173] In the post-development exposure process, it is sufficient to expose at least a portion of the pattern obtained in the development process, but it is preferable to expose the entire pattern.

[0174] The exposure amount in the post-development exposure process, converted from the exposure energy at the wavelength where the photosensitive compound is sensitive, is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0175] The post-development exposure process can be performed using the light source described in the above-mentioned exposure process, preferably broadband light.

[0176] <Metal Layer Formation Process>

[0177] The pattern obtained by the electromagnetic wave irradiation process can be used in the metal layer forming process of forming a metal layer on the pattern.

[0178] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step, which forms a metal layer on a pattern obtained by an electromagnetic wave irradiation step.

[0179] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, and copper is even more preferred.

[0180] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electrolytic plating can be cited. As a preferred method of electrolytic plating, electrolytic plating using copper sulfate or copper cyanide plating solutions can be cited.

[0181] The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[0182] <Cured product>

[0183] The method for manufacturing cured products according to the present invention enables the acquisition of cured products.

[0184] The form of the cured product is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product obtained is preferably in the form of a film.

[0185] Furthermore, by patterning the photosensitive composition, the shape of the cured material can be selected according to its intended use, such as forming a protective film on the wall surface, creating beer halls for conduction, adjusting impedance or capacitance, or imparting heat dissipation. The film thickness of the cured material (the film formed by the cured material) is preferably 0.5 μm or more and 150 μm or less.

[0186] When a cured material is manufactured using the curing method of the present invention, the shrinkage rate is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Herein, the shrinkage rate refers to the percentage change in volume of the pattern after the electromagnetic wave irradiation process relative to the pattern after the development process, and can be calculated using the following formula.

[0187] Shrinkage rate [%] = 100 - (Volume of pattern after electromagnetic wave irradiation ÷ Volume of pattern after development) × 100

[0188] <Properties of cured products>

[0189] When the photosensitive composition used in the method for manufacturing the cured product of the present invention contains a precursor of the cyclized resin described later, from the viewpoint of the elongation at break of the cured product, the cyclization rate in the cured product obtained by the method for manufacturing the cured product of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0190] The elongation at break of the cured product obtained by the manufacturing method of the cured product of the present invention is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.

[0191] The glass transition temperature (Tg) of the cured product obtained by the method of manufacturing the cured product of the present invention is preferably greater than 180°C, more preferably greater than 200°C, and even more preferably greater than 230°C.

[0192] <Application>

[0193] Examples of applications applicable to the manufacturing method of the cured product of the present invention, or to cured products obtained by the manufacturing method of the cured product of the present invention, include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and cases where patterns are formed by etching insulating films used in practical mounting applications as described above. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide / Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0194] Furthermore, the method for manufacturing the cured product of the present invention, or the cured product obtained by the method for manufacturing the cured product of the present invention, can also be used in the manufacture of offset printing plates or screen printing plates, for etching and forming parts, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0195] (Laminated bodies and methods for manufacturing laminated bodies)

[0196] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[0197] The laminate of the present invention is a laminate comprising two or more layers formed of a cured material, and may also be a laminate consisting of three or more layers.

[0198] In the above-described laminate, at least one of the two or more layers formed by the cured material is a layer formed by the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material accompanied by the shrinkage, it is also preferable that all the layers formed by the cured material included in the above-described laminate are layers formed by the cured material of the present invention.

[0199] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the cured product of the present invention, and more preferably includes the steps of repeating the method for manufacturing the laminate of the present invention multiple times.

[0200] The laminate of the present invention preferably comprises two or more layers formed of a cured material, with a metal layer between any one of the layers formed of the cured material. Regarding the metal layer, it is preferable that it is formed by the aforementioned metal layer forming process.

[0201] That is, the method for manufacturing the laminate of the present invention preferably includes, between multiple processes of manufacturing a cured product, a metal layer forming step in which a metal layer is formed on a layer formed from the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0202] As an example of the aforementioned laminate, a preferred laminate may be a laminate containing at least three layers stacked sequentially: a first layer formed of a cured material, a metal layer, and a second layer formed of a cured material.

[0203] The first layer and the second layer formed by the cured material described above are preferably both layers formed by the cured material of the present invention. The photosensitive composition used to form the first layer formed by the cured material and the photosensitive composition used to form the second layer formed by the cured material can be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0204] <Layering Process>

[0205] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0206] The lamination process includes a series of steps, namely (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) an electromagnetic wave irradiation step, performed sequentially on the surface of the pattern (resin layer) or metal layer. Alternatively, at least one of (a) the film formation step and (d) the electromagnetic wave irradiation step may be repeated. Furthermore, after the (d) electromagnetic wave irradiation step, a (e) metal layer formation step may be included. It is self-evident that the lamination process may further appropriately include the aforementioned drying step, etc.

[0207] If a further lamination process is performed after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned electromagnetic wave irradiation process, or the aforementioned metal layer formation process. Plasma treatment can be exemplified as a surface activation treatment. Details of the surface activation treatment will be described later.

[0208] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0209] For example, a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer configuration is preferred, with the resin layer having 2 or more layers and 20 or fewer layers, and more preferably 2 or more layers and 9 or fewer layers.

[0210] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0211] In this invention, it is particularly preferred to form the layer formed from the cured material by further covering the metal layer after the metal layer has been applied. Specifically, examples include repeating (a) the film formation step, (b) the exposure step, (c) the development step, (d) the electromagnetic wave irradiation step, and (e) the metal layer formation step in sequence, or repeating (a) the film formation step, (d) the electromagnetic wave irradiation step, and (e) the metal layer formation step in sequence. By alternately performing the layering step of the cured material and the metal layer formation step, the layer formed from the cured material of this invention and the metal layer can be alternately layered.

[0212] (Surface activation treatment process)

[0213] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the layer formed by the cured material.

[0214] The surface activation process is usually performed after the metal layer formation process, but it can also be performed after the development process described above, by performing a surface activation process on the layer formed from the cured material and then performing the metal layer formation process.

[0215] Regarding the surface activation treatment, it can be performed on at least a portion of the metal layer, on at least a portion of the cured layer, or on at least a portion of both the metal layer and the cured layer. Preferably, at least a portion of the metal layer is surface activated; more preferably, a portion or all of the region of the metal layer on which the cured layer is formed is surface activated. Thus, by surface-activating the surface of the metal layer, the adhesion to the cured layer disposed on its surface can be improved.

[0216] Furthermore, it is preferable to also perform surface activation treatment on part or all of the layer formed by the cured material. In this way, by performing surface activation treatment on the surface of the layer formed by the cured material, the adhesion to the metal layer and resin layer disposed on the surface-activated surface can be improved. In particular, when the layer formed by the cured material is cured by negative development or other methods, it is less likely to be damaged by the surface treatment, thereby easily improving the adhesion.

[0217] As a surface activation treatment, specifically, plasma treatment, corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3, NF3 / O2, surface treatment based on ultraviolet (UV) ozone method, immersion treatment in hydrochloric acid aqueous solution to remove oxide film followed by immersion in organic surface treatment agent containing compounds having at least one amino and thiol group, mechanical roughening treatment using a brush, preferably plasma treatment, and particularly preferably oxygen plasma treatment using oxygen as the raw gas. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J / m³. 2 More preferably, it is 1000 to 100,000 J / m 2 Especially preferred is 10,000 to 50,000 J / m 2 .

[0218] (Semiconductor device manufacturing methods)

[0219] The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing the cured product of the present invention or the method for manufacturing the laminate of the present invention. As a specific example of using the method for manufacturing the cured product of the present invention in the formation of an interlayer insulating film for a redistribution layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in FIG1, and these contents are incorporated herein by reference.

[0220] (Photosensitive composition)

[0221] The photosensitive composition is a composition used to form a photosensitive film in the film-forming step of the method for manufacturing the cured product of the present invention.

[0222] The photosensitive composition preferably contains a curable resin, and more preferably a thermosetting resin.

[0223] Furthermore, the photosensitive composition preferably comprises at least one resin selected from polyimide precursor, polybenzoxazole precursor, polyamide-imide precursor, epoxy resin and phenolic resin (hereinafter also referred to as "specific resin"). More preferably, it comprises at least one resin selected from polyimide precursor, polybenzoxazole precursor and polyamide-imide precursor.

[0224] The photosensitive composition preferably contains the polymeric compound described later.

[0225] Furthermore, the photosensitive composition preferably contains a photopolymerization initiator or a photoacid generator, as described later.

[0226] The following is a detailed description of the components contained in the photosensitizing composition.

[0227] <Specific Resin>

[0228] The photosensitive composition preferably comprises at least one resin selected from polyimide precursors, polybenzoxazole precursors, polyamide-imide precursors, epoxy resins and phenolic resins (“specific resin”).

[0229] The photosensitive composition preferably contains at least one resin selected from polyimide precursor, polybenzoxazole precursor and polyamide-imide precursor as a specific resin, and more preferably contains a polyimide precursor as a specific resin.

[0230] Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0231] In particular, when a particular resin has a free radical polymerizable group, the photosensitive composition preferably contains the free radical polymerization initiator described later, more preferably it contains both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, if necessary, the sensitizer described later can be included. A negative photosensitive film can be formed from such a photosensitive composition, for example.

[0232] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0233] When a particular resin has an acid-degrading group, the photosensitive composition preferably contains a photoacid-generating agent, as described later. Such a photosensitive composition can, for example, form a chemically amplified positive or negative photosensitive film.

[0234] [Polyimide precursor]

[0235] The type of polyimide precursor used in this invention is not particularly specified, but it is preferred to include repeating units represented by the following formula (2).

[0236] [Chemical Formula 1]

[0237]

[0238] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0239] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, preferably an oxygen atom.

[0240] R in equation (2) 111 This refers to a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups comprising aromatic groups with 6 to 20 carbon atoms. The aforementioned straight-chain or branched aliphatic groups can be substituted with groups whose hydrocarbon groups in the chain contain heteroatoms, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups whose cyclic hydrocarbon groups contain heteroatoms. As a preferred embodiment of the invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with groups represented by -Ar-L-Ar- being particularly preferred. Wherein, Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Their preferred ranges are as described above.

[0241] R 111 The preferred derivative is a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more may be used.

[0242] Specifically, diamines preferably contain a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof; more preferably, diamines contain an aromatic group with 6 to 20 carbon atoms. The aforementioned straight-chain or branched aliphatic group can be substituted with a group whose hydrocarbon group in the chain contains a heteroatom, and the aforementioned cyclic aliphatic group and aromatic group can be substituted with a group whose cyclic hydrocarbon group contains a heteroatom. Examples of groups containing aromatic groups are as follows.

[0243] [Chemical Formula 2]

[0244]

[0245] In the formula, A represents a single bond or a divalent linker, preferably a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a group selected from alkylene groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0246] In the formula, * indicates the bonding position with other structures.

[0247] As a diamine, specifically, examples 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 isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diamino... 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 ether and 3,3'-diaminodiphenyl ether, 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'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminofluorene, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)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-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl At least one diamine selected from the following: 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0248] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0249] Furthermore, a diamine having two or more alkylene glycol units as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 on the main chain may also be preferred.

[0250] From the perspective of the flexibility of the obtained organic membrane, R 111Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0251] Furthermore, considering i-ray transmittance, R 111 Preferably, it is a divalent organogroup represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferred to be a divalent organogroup represented by formula (61).

[0252] Equation (51)

[0253] [Chemical Formula 3]

[0254]

[0255] In equation (51), R 50 ~R 57 R can be an organic group that is independently composed of a hydrogen atom, a fluorine atom, or a monovalent organic group. 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * represents the bonding position with the nitrogen atom in formula (2) independently.

[0256] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0257] [Chemical Formula 4]

[0258]

[0259] In equation (61), R 58 and R 59 Each of the following is independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding position with the nitrogen atom in formula (2).

[0260] Examples of diamines providing the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used in combination.

[0261] R in equation (2) 115 The organovalent group is indicated. Preferably, the organovalent group is a tetravalent organovalent group containing an aromatic ring, and more preferably, it is a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently indicates the bonding position with other structures.

[0262] [Chemical Formula 5]

[0263]

[0264] In equation (5), R 112 It is a single bond or a divalent linker, preferably a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO- and combinations thereof, more preferably a group selected from alkylene groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0265] Regarding R 115 Specifically, examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic dianhydrides. As for R... 115 The corresponding structure of the polyimide precursor can contain only one type of tetracarboxylic acid dianhydride residue, or it can contain two or more types.

[0266] Tetracarboxylic acid dianhydride is preferably represented by the following formula (0).

[0267] [Chemical Formula 6]

[0268]

[0269] In equation (0), R 115 R represents a tetravalent organogroup. 115 The preferred range is the same as R in equation (2). 115 The meanings are the same, and the preferred ranges are also the same.

[0270] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-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'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propanedihydride. Anhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride and these alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0271] Furthermore, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as preferred examples.

[0272] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0273] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organogroup. As a monovalent organogroup, it is preferred to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymerizable group, more preferably both contain polymerizable groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of cross-linking through the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxybutyl, benzoxazolyl, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred.

[0274] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0275] [Chemical Formula 7]

[0276]

[0277] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0278] In equation (III), * indicates the bonding position with other structures.

[0279] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0280] Preferred R 201 Examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds, more preferably alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds, and even more preferably alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0281] In this invention, polyalkoxide refers to an alkoxide group directly bonded to two or more groups. The alkylene groups in the multiple alkoxide groups contained in a polyalkoxide group may be the same or different.

[0282] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0283] The number of carbon atoms in the alkylene group (the number of carbon atoms including the substituent if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and especially preferably 2.

[0284] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0285] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0286] From the viewpoint of solvent solubility and solvent resistance, polyoxyethylene, polypropylene, polytrimethylene, polytetramethethylene, or groups obtained by bonding multiple ethyleneoxy groups with multiple propyleneoxy groups are preferred as polyoxyethylene or polypropyleneoxy groups, and polyoxyethylene is even more preferred. In the groups obtained by bonding multiple ethyleneoxy groups with multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the number of repetitions of ethyleneoxy groups in these groups is as described above.

[0287] In equation (2), in R 113 In the case of hydrogen atoms or in R 114 In the case of hydrogen atoms, polyimide precursors can form countersalts with tertiary amine compounds having vinyl unsaturated bonds. An example of such a tertiary amine compound with vinyl unsaturated bonds is N,N-dimethylaminopropyl methacrylate.

[0288] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is an acid-degradable group that decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0289] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0290] Furthermore, it is also preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0291] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0292] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferred that at least one of the polyimide precursors used in this invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased.

[0293] Equation (2-A)

[0294] [Chemical Formula 8]

[0295]

[0296] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organogroup, R 113 and R 114 R represents either a hydrogen atom or a monovalent organic group independently. 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both are groups containing polymerizable groups.

[0297] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0298] R 112 R in equation (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0299] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it is self-evident that the polyimide precursor may contain other types of repeating units besides the repeating unit of formula (2) mentioned above.

[0300] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content, and all repeating units in the polyimide precursor except for the end units can also be repeating units represented by formula (2).

[0301] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0302] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0303] In this specification, the molecular weight dispersion is a value calculated using weight-average molecular weight / number-average molecular weight.

[0304] Furthermore, when the photosensitive composition contains multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0305] [Polybenzoxazole precursor]

[0306] There are no particular provisions regarding the structure of the polybenzoxazole precursor used in this invention, but it is preferred to include repeating units represented by the following formula (3).

[0307] [Chemical Formula 9]

[0308]

[0309] In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0310] In equation (3), R 123 and R 124 respectively with R in equation (2) 113 The meanings are the same, and the preferred ranges are also the same. That is, at least one of them is preferably a polymeric group.

[0311] In equation (3), R 121 This indicates a divalent organogroup. Preferably, the divalent organogroup comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 The preferred choice is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0312] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred.

[0313] As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is more preferred. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkylene group.

[0314] Examples of dicarboxylic acids containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetrafluoroadipic acid. Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and dicarboxylic acids represented by the following formula, etc.

[0315] [Chemical Formula 10]

[0316]

[0317] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0318] As a dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and more preferably dicarboxylic acids consisting only of the following groups having an aromatic group and two -COOH groups.

[0319] [Chemical Formula 11]

[0320]

[0321] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * independently represents the bonding position with other structures.

[0322] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and phthalic acid.

[0323] In equation (3), R 122 This represents a tetravalent organogroup. As a tetravalent organogroup, it corresponds to R in equation (2) above. 115 The meanings are the same, and the preferred ranges are also the same.

[0324] R 122 Preferably, the group is derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4-amino-4-hydroxyphenyl)hexafluoropropane. (-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These groups derived from diaminophenol derivatives can be used alone or in combination.

[0325] Among the diaminophenol derivatives, the following diaminophenol derivatives having aromatic groups are preferred.

[0326] [Chemical Formula 12]

[0327]

[0328] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, and * and # represent the bonding positions with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Furthermore, R... 122 The structure represented by the above formula is also preferred. In R 122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferable that any 2 are R in formula (3). 122 The bonding positions of the nitrogen atoms and the other two are related to R in equation (3). 122 The bonding positions of the bonded oxygen atoms are preferably two associating with R in equation (3). 122 The bonding positions of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding positions of the nitrogen atoms, or the two asterisks (*) are related to R in equation (3). 122 The bonding positions of the nitrogen atoms and the two #'s are related to R in equation (3). 122The bonding positions of the bonded oxygen atoms are further preferably two as R in equation (3). 122 The bonding positions of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding positions of the nitrogen atoms.

[0329] The diaminophenol derivative is also preferably a compound represented by formula (As).

[0330] [Chemical Formula 13]

[0331]

[0332] In formula (As), R1 is an organogroup selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the group consisting of the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl, alkoxy, acyloxy, or cyclic alkyl, which may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl, alkoxy, acyloxy, or cyclic alkyl, which may be the same or different.

[0333] [Chemical Formula 14]

[0334]

[0335] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0336] In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R3, would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, which is particularly preferred in terms of further improving the effect of achieving a high cyclization rate when cured at low temperature.

[0337] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it can maintain high transparency to i-rays and achieve a high cyclization rate when cured at low temperature, which is therefore preferred.

[0338] Furthermore, in the above formula (As), R1 is preferably an alkylene or substituted alkylene. Specific examples of the alkylene or substituted alkylene involved in R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of achieving a good balance between maintaining high transparency to i-rays and high cyclization rate during low-temperature curing, while also obtaining a polybenzoxazole precursor with sufficient solubility in solvents.

[0339] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated into this specification.

[0340] As a specific example of the structure of the diaminophenol derivative represented by the above formula (As), the structure described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506 can be cited, and such content is incorporated into this specification. Of course, it is self-evident that it is not limited to these.

[0341] In addition to the repeating unit in formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.

[0342] In terms of suppressing warping associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0343] [Chemical Formula 15]

[0344]

[0345] In equation (SL), Z has structures a and b, and R 12 R is a hydrocarbon group consisting of 1 to 10 hydrogen atoms or carbon atoms. 2s R is a hydrocarbon group with 1 to 10 carbon atoms. 3s R 4s R 5s R 6s At least one of the radicals is an aromatic group, and the rest are organic groups consisting of hydrogen atoms or 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, structure a is 5–95 mol%, structure b is 95–5 mol%, and a+b is 100 mol%.

[0346] In equation (SL), Z, as a preferred option, can be represented by R in structure b. 5s and R 6s The structure is phenyl. Furthermore, the molecular weight of the structure shown in formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, achieving both the effect of suppressing warpage and improving solvent solubility.

[0347] In cases where the diamine residue represented by formula (SL) is used as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R in formula (2). 115 Examples.

[0348] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0349] The molecular weight dispersion of the aforementioned polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzoxazole precursor; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0350] Furthermore, when the photosensitive composition contains multiple polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polybenzoxazole precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated using the multiple polybenzoxazole precursors as a single resin are each within the aforementioned ranges.

[0351] [Polyamide-imide precursor]

[0352] The polyamide-imide precursor preferably comprises repeating units represented by the following formula (PAI-2).

[0353] [Chemical Formula 16]

[0354]

[0355] In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 It represents a hydrogen atom or an organic group with a valence of 1.

[0356] In formula (PAI-2), R 117Examples of possible groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups obtained by linking two or more of these groups through single bonds or linking groups. Preferably, the groups are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups through single bonds or linking groups. More preferably, the groups are aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0357] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, haloalkylene, aryl, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, haloalkylene, aryl, or linking groups formed by bonding two or more of these are more preferred.

[0358] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0359] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0360] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0361] Furthermore, R is preferred. 117 Derived from tricarboxylic acid compounds whose at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation method described above.

[0362] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0363] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0364] Examples of tricarboxylic acid compounds that can be halogenated and used in the manufacture of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0365] These tricarboxylic acid compounds can be used in one or more forms.

[0366] Specifically, as a tricarboxylic acid compound, it is preferable to be a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound obtained by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through single bonds or linking groups.

[0367] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide.

[0368] These compounds can be compounds with two carboxyl groups anhydride-substituted (e.g., trimellitic anhydride) or compounds with at least one carboxyl group halogenated (e.g., trimellitic anhydride acyl chloride).

[0369] In formula (PAI-2), R 111 A 2 R 113 respectively with R in the above formula (2) 111 A 2 R 113 The meanings are the same, and the preferred methods are also the same.

[0370] The polyamide-imide precursor may further contain other repeating units.

[0371] Other repeating units can be exemplified by the repeating unit represented by equation (2) above, the repeating unit represented by equation (PAI-1) below, etc.

[0372] [Chemical Formula 17]

[0373]

[0374] In formula (PAI-1), R 116 R represents a divalent organic group. 111 This indicates a divalent organic group.

[0375] In formula (PAI-1), R 116Examples of possible groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups obtained by linking two or more of these groups through single bonds or linking groups. Preferably, the groups are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more of these groups through single bonds or linking groups. More preferably, the groups are aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0376] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, haloalkylene, aryl, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, haloalkylene, aryl, or linking groups formed by bonding two or more of these are more preferred.

[0377] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0378] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0379] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0380] Furthermore, R 116 Preferably derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0381] In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound.

[0382] In dicarboxylic acid dihalides, the carboxyl group only needs to be halogenated, for example, preferably chlorinated. That is, dicarboxylic acid dihalides are preferably dicarboxylic acid dichlorides.

[0383] Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that can be halogenated and used in the manufacture of polyamide-imide precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0384] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0385] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable to be a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through single bonds or linking groups. More preferably, it is a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through single bonds or linking groups.

[0386] Furthermore, specific examples of dicarboxylic acid compounds 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, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, etc. Acid, hexafluorosebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, henodecanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentadecanedioic acid, Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontandioic acid, triacontandioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyl diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0387] As a specific example of a dicarboxylic acid dihalide compound, one can cite a compound formed by halogenating two carboxyl groups from the above-mentioned dicarboxylic acid compound examples.

[0388] In formula (PAI-1), R 111 R in equation (2) above 111The meanings are the same, and the preferred methods are also the same.

[0389] Furthermore, the polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0390] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as the diamine component can be cited.

[0391] As one embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2).

[0392] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2) or formula (PAI-1).

[0393] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0394] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the photosensitive composition contains multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersion of at least one polyamide-imide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersion calculated when the multiple polyamide-imide precursors are considered as a single resin are each within the above-mentioned ranges.

[0395] [Methods for manufacturing polyimide precursors, etc.]

[0396] Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid and then esterifying it with a condensing agent or alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine, etc. In the above manufacturing methods, it is more preferable to obtain a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine.

[0397] Examples of condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0398] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0399] Examples of halogenating agents mentioned above include thioyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0400] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0401] As an organic solvent, it can be appropriately selected according to the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0402] In methods for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0403] The basic compound can be appropriately set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0404] -End- Capping Agent-

[0405] In methods for manufacturing polyimide precursors, etc., to further improve storage stability, it is preferable to seal the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the polyimide precursor, etc. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc. From the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are more preferred. Preferred monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenols, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0406] Furthermore, when sealing the amino group at the end of the resin, a compound having a functional group capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, and benzoyl chloride.

[0407] -Solid precipitation-

[0408] In the manufacture of polyimide precursors, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer component to precipitate as a solid and then dried, thereby obtaining the polyimide precursor. To improve the purification degree, the operations of re-dissolving, re-precipitating, and drying the polyimide precursor may be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0409] [Epoxy Resin]

[0410] There are no particular limitations on epoxy resins, but examples include phenolic varnish-type epoxy resins, bisphenol-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ether-type epoxy resins, pyrrolimethane-type epoxy resins, pyrrolimethane-type epoxy resins, alkyl-modified pyrrolimethane-type epoxy resins, epoxy resins containing triazine cores, dicyclopentadiene-modified phenolic-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, phenolic aralkyl-type epoxy resins having at least one of a phenylene skeleton and a biphenylene skeleton, aralkyl-type epoxy resins having at least one of a phenylene skeleton and a biphenylene skeleton, and aliphatic epoxy resins, etc.

[0411] Furthermore, in cases where a particular resin contains an epoxy resin, the epoxy compound described in the following polymerizable compounds may be used as the particular resin.

[0412] [Phenolic resin]

[0413] Examples of phenolic resins include phenolic varnish resins and vinyl polymers.

[0414] Examples of phenolic varnish resins include resins obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, or bisphenol A.

[0415] Examples of aldehydes mentioned above include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.

[0416] The above-mentioned phenols and aldehydes can be used alone or in combination of two or more.

[0417] Specific examples of the aforementioned phenolic varnish resins include, for instance, m-cresol, p-cresol, or the condensation products of these mixtures with formalin.

[0418] The molecular weight distribution of the aforementioned phenolic varnish resin can be adjusted using methods such as classification. Furthermore, low molecular weight components containing phenolic hydroxyl groups such as bisphenol C or bisphenol A can be mixed with the aforementioned phenolic varnish resin.

[0419] 〔content〕

[0420] The content of a specific resin in the photosensitive composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solids content of the photosensitive composition. Furthermore, the content of the resin in the photosensitive composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the photosensitive composition.

[0421] The photosensitive composition may contain only one specific resin or two or more. When two or more resins are contained, the total amount is preferably within the range described above.

[0422] Furthermore, it is also preferred that the photosensitive composition contains at least two resins.

[0423] Specifically, the photosensitive composition may contain a total of two or more specific resins and other resins described below, or it may contain two or more specific resins, but preferably it contains two or more specific resins.

[0424] When the photosensitive composition contains two or more specific resins, for example, it is preferable to contain a polyimide precursor and a structure derived from a dianhydride (R as described in formula (2) above). 115 Two or more different polyimide precursors.

[0425] <Other Resins>

[0426] The photosensitive composition may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0427] Other examples of resins include polyamides, polysiloxanes, resins with siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, polyurethane resins, butyral resins, styrene resins, polyether resins, polyester resins, etc.

[0428] For example, by further adding (meth)acrylic resin, a photosensitive composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0429] For example, instead of the polymerizable compounds described later, or other polymerizable compounds described later, a polymerizable group with a high polymerizable group value (e.g., the molar amount of polymerizable groups in 1 g of resin is 1 × 10⁻⁶) with a weight average molecular weight of 20,000 or less can be used. -3 Adding (meth)acrylic resin at a molar ratio of 1 g or higher to the photosensitive composition can improve the coatability of the photosensitive composition, the solvent resistance of the pattern (cured product), etc.

[0430] When the photosensitive composition contains other resins, the content of the other resins relative to the total solids content of the photosensitive composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0431] Furthermore, the content of other resins in the photosensitive composition is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the photosensitive composition.

[0432] Furthermore, as a preferred embodiment of the photosensitive composition, it is also possible to set the content of other resins to be low. In the above embodiment, the content of other resins relative to the total solids content of the photosensitive composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0433] The photosensitive composition may contain only one other resin or two or more. When two or more resins are contained, the total amount is preferably within the range described above.

[0434] <Polymerizing compounds>

[0435] The photosensitive composition preferably contains a polymeric compound.

[0436] Furthermore, the photosensitive composition preferably contains a polymeric compound with two or more functions, and containing a polymeric compound with three or more functions is also a preferred option.

[0437] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0438] [Free radical crosslinking agent]

[0439] The photosensitive composition preferably contains a free radical crosslinking agent.

[0440] The free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group contains a group with an ethylene unsaturated bond. Examples of such groups containing an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido groups.

[0441] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred as the groups containing ethylene unsaturated bonds, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0442] The free radical crosslinking agent is preferably a compound having one or more vinyl unsaturated bonds, but more preferably a compound having two or more. The free radical crosslinking agent may have three or more vinyl unsaturated bonds.

[0443] As for the above-mentioned compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred.

[0444] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the photosensitive composition preferably includes a compound having two vinyl unsaturated bonds and the aforementioned compound having three or more vinyl unsaturated bonds.

[0445] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0446] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Additionally, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogroups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used to replace the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and these contents are incorporated into this specification.

[0447] Furthermore, the free radical crosslinking agent is preferably a compound with a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl)isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate addition. Compounds obtained by esterification, such as urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth)acrylic acid, and other polyfunctional acrylates or methacrylates and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Additionally, polyfunctional (meth)acrylates obtained by reacting compounds having cyclic ether groups and vinyl unsaturated bonds, such as glycidyl methacrylate, with polyfunctional carboxylic acids can also be cited.

[0448] Furthermore, as preferred free radical crosslinking agents besides those described above, compounds having a fluorene ring and having two or more groups containing ethylene unsaturated bonds, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

[0449] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Furthermore, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, compounds described as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0450] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 may also be used, and these contents are incorporated into this specification.

[0451] Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compound, which is described together with specific examples as formula (1) and formula (2), can also be used as a free radical crosslinking agent. This compound is obtained by (meth)acrylate esterification after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0452] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and these contents are incorporated into this specification.

[0453] As free radical crosslinking agents, preferred products include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., or A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., or A-DPH: manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. These oligomer types can also be used.

[0454] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methyl acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentyli groups, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyryliyl groups, manufactured by Nippon Kayaku Co., Ltd.; urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (manufactured by 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.

[0455] As free radical crosslinking agents, urethane acrylate compounds having an ethylene oxide backbone, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418, are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0456] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has obtained acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is a free radical crosslinking agent that has obtained acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is a pentaerythritol or dipentaerythritol compound. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., such as M-510 and M-520.

[0457] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the manufacturing process is excellent, and consequently, the developability is excellent. Furthermore, the polymerizability is good. The acid value is determined according to the description in JIS K 0070:1992.

[0458] From the viewpoint of pattern resolution and film stretchability, the photosensitive composition preferably uses a difunctional methacrylate or acrylate.

[0459] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Methacrylates, dimethyloltricyclodecane diacrylates, dimethyloltricyclodecane dimethacrylates, bisphenol A EO (ethylene oxide) adduct diacrylates, bisphenol A EO adduct dimethacrylates, bisphenol A PO (propylene oxide) adduct diacrylates, bisphenol A PO adduct dimethacrylates, 2-hydroxy-3-acryloyloxypropyl methacrylates, cyanuric acid EO-modified diacrylates, cyanuric acid-modified dimethacrylates, difunctional acrylates with other urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0460] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the molecular weight of the polyethylene glycol chain is around 200.

[0461] Regarding photosensitive compositions, from the viewpoint of suppressing warping by controlling the elastic modulus of the accompanying pattern (cured product), a monofunctional free radical crosslinking agent can preferably be used as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are 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-vinyl caprolactam, and other N-vinyl compounds, alkenyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred.

[0462] In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be used as free radical crosslinking agents with two or more functions.

[0463] When a free radical crosslinking agent is included, its content relative to the total solids content of the photosensitive composition is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0464] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used simultaneously, their combined dosage is preferably within the range described above.

[0465] [Other crosslinking agents]

[0466] The photosensitive composition also preferably contains other crosslinking agents that are different from the free radical crosslinking agents described above.

[0467] In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. Preferably, they are compounds having a plurality of groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by photosensitization by the photoacid generator or photoalkali generator described above. More preferably, they are compounds having a plurality of groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by the action of an acid or base.

[0468] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0469] As other crosslinking agents, compounds having at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0470] Other crosslinking agents include, for example, compounds having a structure in which the hydrogen atoms of the amino groups are replaced by acyloxymethyl, hydroxymethyl, or alkoxymethyl groups by reacting formaldehyde or formaldehyde and alcohol with melamine, glycourea, urea, alkylene urea, benzoguanamine, or other amino-containing compounds. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used.

[0471] Crosslinking agents that use melamine as an amino-containing compound are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkylene urea are called urea-based crosslinking agents; crosslinking agents that use alkylene urea are called alkylene urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents.

[0472] Among these, the photosensitive composition preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents (described later).

[0473] Examples of compounds containing at least one of the alkoxymethyl and acylmethyl groups of the present invention include compounds in which the alkoxymethyl or acylmethyl group is directly substituted on the nitrogen atom of an aromatic group or a urea structure described below, or on a triazine group.

[0474] The alkoxymethyl or acylmethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.

[0475] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0476] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0477] [Chemical Formula 18]

[0478]

[0479] R 100 Indicates alkyl or acyl groups.

[0480] R 101 and R 102 Each organic group can independently represent a monovalent organic group and can bond with each other to form a ring.

[0481] As compounds in which alkoxymethyl or acylmethyl groups are directly substituted on an aromatic group, examples include various compounds of the following general formula.

[0482] [Chemical Formula 19]

[0483]

[0484] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 This refers to a group that represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce a base-soluble group (e.g., a group that is removed by the action of an acid, -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5 This indicates a group that is released through the action of an acid.

[0485] R 105 Each can independently represent an alkyl or alkenyl group, where a, b, and c are each 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0486] Groups that decompose under acidic conditions to produce alkali-soluble groups, groups that are removed under acidic conditions, and -C(R) groups. 4 )2COOR 5 The R in the represented group 5 For example, -C(R) can be cited. 36 (R) 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (OR) 39 )wait.

[0487] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0488] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0489] The aforementioned alkyl group can be either straight-chain or branched.

[0490] As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

[0491] The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as fused rings.

[0492] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0493] As the aforementioned aralkyl group, aralkyl groups with 7 to 20 carbon atoms are preferred, and aralkyl groups with 7 to 16 carbon atoms are more preferred.

[0494] The aryl group mentioned above refers to an aryl group that has been substituted with an alkyl group, and the preferred methods for these alkyl and aryl groups are the same as those for the alkyl and aryl groups mentioned above.

[0495] The alkenyl group mentioned above is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0496] Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0497] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0498] These groups are preferably tertiary alkyl esters, acetals, cumyl esters, enols, etc. Tertiary alkyl esters and acetals are more preferred.

[0499] Specifically, the following structures can be cited as examples of compounds having an alkoxymethyl group. Regarding compounds having an acylmethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group can be cited. Various compounds can be cited as examples of compounds having an alkoxymethyl group or an acylmethyl group intramolecularly, but are not limited to these.

[0500] [Chemical Formula 20]

[0501]

[0502] [Chemical Formula 21]

[0503]

[0504] For compounds containing at least one of alkoxymethyl and acylmethyl groups, commercially available compounds or compounds synthesized by known methods may be used.

[0505] From the viewpoint of heat resistance, compounds in which alkoxymethyl or acylmethyl groups are directly substituted on the aromatic ring or triazine ring are preferred.

[0506] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0507] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc.

[0508] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0509] Monohydroxymethylated ethionide or dihydroxymethylated ethionide, monomethoxymethylated ethionide, dimethoxymethylated ethionide, monoethoxymethylated ethionide, diethoxymethylated ethionide, monopropoxymethylated ethionide, dipropoxymethylated ethionide, monobutoxymethylated ethionide or dibutoxymethylated ethionide, etc., are ethionide-based crosslinking agents.

[0510] Propaneide-based crosslinking agents, including monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea.

[0511] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolone, etc.

[0512] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0513] In addition, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, a compound having at least one group selected from hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) may also be preferred.

[0514] Specific examples of such compounds include benzyl 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, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0515] Other commercially available crosslinking agents can also be used. Preferred commercially available agents include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0516] Furthermore, it is also preferred that the photosensitive composition contains at least one compound selected from epoxy compounds, cyclobutane compounds and benzoxazine compounds as other crosslinking agents.

[0517] -Epoxy compounds (compounds containing epoxy groups)-

[0518] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warping of the photosensitive composition.

[0519] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to a polyethylene oxide compound with 2 or more repeating units of ethylene oxide, preferably with 2 to 15 repeating units.

[0520] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones with epoxy groups such as polymethyl(glycidyloxypropyl)siloxane, but these are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-30 00-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 (these are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used preferably.

[0521] [Chemical Formula 22]

[0522]

[0523] In the formula, n is an integer from 1 to 5 and m is an integer from 1 to 20.

[0524] In the above structure, considering both heat resistance and elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[0525] -Oxycyclic butane compounds (compounds containing oxycyclic butane groups)-

[0526] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutane)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. is preferably used; these can be used alone or in combination of two or more.

[0527] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0528] Since the crosslinking reaction is caused by the ring-opening addition reaction, the benzoxazine compound does not produce degassing during curing, thereby further reducing thermal shrinkage and inhibiting warping, and is therefore preferred.

[0529] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are product names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resin, and phenolic varnish-type dihydrobenzoxazine compounds. These can be used alone or in combination of two or more.

[0530] The content of other crosslinking agents relative to the total solids content of the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may be two or more types. When two or more other crosslinking agents are contained, their total content is preferably within the above range.

[0531] Organometallic complexes

[0532] From the viewpoint of chemical resistance, photosensitizing compositions preferably contain organometallic complexes.

[0533] Organometallic complexes are any organic complexes containing metal atoms, but are preferably complexes containing metal atoms and organic groups, more preferably compounds in which the organic groups coordinate to the metal atoms, and even more preferably metallocene compounds.

[0534] In this invention, metallocene compounds refer to organometallic complexes having two cyclopentadienyl anionic derivatives that can have substituents as η5-ligands.

[0535] There are no particular limitations on the aforementioned organic groups, but hydrocarbon groups or groups composed of hydrocarbon groups and heteroatoms are preferred. As heteroatoms, oxygen atoms, sulfur atoms, and nitrogen atoms are preferred.

[0536] In this invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferably at least two of them are cyclic groups.

[0537] The aforementioned cyclic base is preferably selected from 5-membered rings and 6-membered rings, and more preferably from 5-membered rings.

[0538] The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred.

[0539] As a cyclic group of a 5-membered ring, cyclopentadienyl is preferred.

[0540] Furthermore, the organometallic complexes used in this invention preferably contain 2 to 4 cyclic groups per molecule.

[0541] The metal contained in the organometallic complex is not particularly limited, but it is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from titanium, zirconium and hafnium, even more preferably at least one metal selected from titanium and zirconium, and particularly preferably titanium.

[0542] Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, but preferably only one metal atom. When an organometallic complex contains two or more metal atoms, it can contain only one type of metal atom, or it can contain two or more types of metal atoms.

[0543] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnium compound, more preferably a titanocene compound, a zirconocene compound, or a hafnium compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0544] The ability of organometallic complexes to initiate photoradical polymerization is also one of the preferred methods of this invention.

[0545] In this invention, having photoradical polymerization initiation capability means being able to generate free radicals that can be initiated into free radical polymerization by light irradiation. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light but the free radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation capability can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it disappears, an appropriate method can be selected according to the type of free radical crosslinking agent, for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography).

[0546] When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconium diacene compound or a hafnium diacene compound, even more preferably a titanocene compound or a zirconium diacene compound, and particularly preferably a titanocene compound.

[0547] When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably selected from at least one compound selected from titanium diacene compounds, tetraalkoxy titanium compounds, acylated titanium compounds, titanium chelates, zirconium diacene compounds, and hafnium diacene compounds, more preferably selected from at least one compound selected from titanium diacene compounds, zirconium diacene compounds, and hafnium diacene compounds, even more preferably selected from at least one compound selected from titanium diacene compounds and zirconium diacene compounds, and particularly preferably titanium diacene compounds.

[0548] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0549] As organometallic complexes, compounds represented by the following formula (P) are preferably examples.

[0550] [Chemical Formula 23]

[0551]

[0552] In formula (P), M is a metal atom, and R are independent substituents.

[0553] Preferably, the R groups mentioned above are independently selected from aromatic groups, alkyl groups, halogen atoms, and alkylsulfonyloxy groups.

[0554] In formula (P), the metal atom represented by M is preferably an iron atom, titanium atom, zirconium atom or hafnium atom, more preferably a titanium atom, zirconium atom or hafnium atom, even more preferably a titanium atom or zirconium atom, and particularly preferably a titanium atom.

[0555] As an aromatic group in R of formula (P), examples include aromatic groups with 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups with 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl.

[0556] The alkyl group in R of formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms, including methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl.

[0557] Examples of halogen atoms in R include F, Cl, Br, and I.

[0558] As the alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R, it is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl.

[0559] The R mentioned above can also have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0560] Specific examples of organometallic complexes are not particularly limited, but examples include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, diisopropoxybis(acetylacetone) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadienyltrimethylethanol titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium and the following compounds.

[0561] [Chemical Formula 24]

[0562]

[0563] In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may be used, but are not limited thereto.

[0564] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solids content of the photosensitive composition. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0565] One or more organometallic complexes can be used. When using two or more, the total amount is preferably within the range described above.

[0566] [Polymerization initiator]

[0567] The photosensitive composition preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it preferably contains a photopolymerization initiator.

[0568] Furthermore, from the viewpoint of the chemical resistance and elongation at break of the cured product, the photosensitive composition of the present invention preferably contains a metallocene compound described later as a polymerization initiator.

[0569] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, an active agent that generates active radicals by interacting with a photoexcited sensitizer may also be used.

[0570] The photoradical polymerization initiator preferably contains at least one initiator with a concentration of at least about 50 L / mol in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 / cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Varian Medical Systems, Inc., Cary-5 spectrophotometer) and with ethyl acetate solvent at a concentration of 0.01 g / L.

[0571] As a photoradical polymerization initiator, any known compound can be used. Examples include haloalkanes (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For details, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples can be cited in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peracid-based initiators described in Japanese Patent Application Publication No. 2019-167313, and these contents are also incorporated into this specification.

[0572] As a ketone compound, examples include the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, and this content is incorporated into this specification. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0573] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated herein by reference.

[0574] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0575] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0576] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0577] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

[0578] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0579] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wide exposure latitude (exposure margin) and also function as photocuring accelerators, making them particularly preferred.

[0580] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science. The compounds described in and Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0581] Preferred oxime compounds include, for example, compounds with the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In photosensitive compositions, oxime compounds (oxime-based photoradical polymerization initiators) are particularly preferred as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker group within the molecule.

[0582] [Chemical Formula 25]

[0583]

[0584] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also acceptable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMERARKEMA) are also acceptable. Furthermore, oxime compounds with the following structures can also be used.

[0585] [Chemical Formula 26]

[0586]

[0587] Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, and these contents are incorporated into this specification.

[0588] As photoradical polymerization initiators, oxime compounds having at least one benzene ring in the carbazole ring forming the naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0589] Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, and these contents are included in this specification.

[0590] Nitro-containing oxime compounds can be used as photopolymerization initiators. Nitro-containing oxime compounds are preferably dimers. Specific examples of nitro-containing oxime compounds include compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012 and 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKACORPORATION) can also be cited as a nitro-containing oxime compound.

[0591] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0592] Oxime compounds obtained by bonding hydroxyl groups to the carbazole skeleton can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, which are included in this specification.

[0593] As a photopolymerization initiator, Ar aromatic cyclic groups with electron-withdrawing groups introduced onto the aromatic ring can also be used. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1 Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups, with acyl and nitro groups being preferred. Acyl groups are more preferred due to their ease of forming films with excellent lightfastness, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acyl, or amino groups, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio, or amino groups being more preferred, and alkoxy, alkylthio, or amino groups being even more preferred.

[0594] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0595] [Chemical Formula 27]

[0596]

[0597] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonoyl, carbamoyl, or aminosulfonyl.

[0598] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0599] R X3 ~R X14 Each can be used independently to represent a hydrogen atom or a substituent;

[0600] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0601] In the above formula, R is preferred. X12 R is an electron-withdrawing group. X10 R X11 R X13 R X14 It is a hydrogen atom.

[0602] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

[0603] Examples of particularly preferred oxime compounds include oxime compounds with specific substituents as shown in Japanese Patent Application Publication No. 2007-269779 or oxime compounds with thioaryl groups as shown in Japanese Patent Application Publication No. 2009-191061, and these contents are incorporated herein by reference.

[0604] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably selected from compounds among trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0605] Further preferred photoradical polymerization initiators are trihalomethane triazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferably, at least one compound is selected from trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. Particularly preferred are metallocene compounds.

[0606] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by ring condensation with aromatic rings 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. Compounds represented by formula (I) below can also be used.

[0607] [Chemical Formula 28]

[0608]

[0609] In equation (I), R I00 The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy or phenyl group having 1 to 12 carbon atoms, or the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, a halogen atom, cyclopentyl, cyclohexyl, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are at least one substituted phenyl or biphenyl group. I01 The group represented by formula (II) or the group with R I00 The same group, R I02 ~R I04 Each is independently an alkyl group, an alkoxy group, or a halogen atom, having 1 to 12 carbon atoms.

[0610] [Chemical Formula 29]

[0611]

[0612] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0613] Furthermore, the photoradical polymerization initiator can also be the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, and this content is incorporated into this specification.

[0614] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like increases, making it less prone to precipitation over time, thereby improving the long-term stability of the photosensitizing composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and (G) described in Japanese Patent Application Publication No. 2013-522445. The oxime ester photoinitiators described in International Publication No. 2016 / 034963, paragraph 0007 of Japanese Patent Publication No. 2017-523465, paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and paragraph 0017-0026 of Japanese Patent Application Publication No. 6469669 are included in this specification.

[0615] When a photopolymerization initiator is included, its content relative to the total solids content of the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may be one type or two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0616] In addition, photopolymerization initiators sometimes function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators is sometimes further carried out by heating in an oven or heating plate.

[0617] [Sensitizer]

[0618] The photosensitizing composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer then comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0619] As usable sensitizers, compounds such as ethanolamine, benzophenone, michalcone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyrrolidone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethine, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0620] Examples of sensitizers include milchone, 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-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminobenzylidene dihydroindone. Hydroindone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 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-dimethyl 3-aminocoumarin, 7-diethylamino-4-methylcoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate Isoamyl 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, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0621] Furthermore, other sensitizing pigments can be used.

[0622] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

[0623] When the photosensitive composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used simultaneously.

[0624] [Chain transfer agent]

[0625] The photosensitive composition may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithioaminocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. In particular, thiols are preferably used.

[0626] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0627] When the photosensitive composition contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the photosensitive composition is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total content is preferably within the above-mentioned range.

[0628] [Photo-acid generator]

[0629] The photosensitizing composition preferably contains a photoacid-producing agent.

[0630] Photoacid generators refer to compounds that produce at least one of Brønsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in conjunction with a sensitizer, photoacid generators that can generate acid upon photosensitization are preferred.

[0631] Examples of acids that can be produced include, preferably, hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, sulfonic acid amides, etc.

[0632] Examples of photoacid generators used in photosensitive compositions include quinone diazide compounds, oxime sulfonate compounds, organohalogenated compounds, organoborate compounds, disulfonic acid compounds, and onium salt compounds.

[0633] From the perspective of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred. From the perspective of the mechanical properties of the formed membrane, oxime esters are preferred.

[0634] Examples of quinone diazide compounds include compounds obtained by attaching a sulfonate bond of quinone diazide to a monovalent or polyvalent hydroxyl group, compounds obtained by attaching a sulfonamide bond of quinone diazide to a monovalent or polyvalent amine group, and compounds obtained by attaching a sulfonate bond and / or a sulfonamide bond of quinone diazide to a polyhydroxy polyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may be unsubstituted with quinone diazide, but it is preferable that an average of 40 mol% or more of the functional groups are substituted with quinone diazide. By containing such a quinone diazide compound, a photosensitive composition capable of sensitizing i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a mercury lamp, which is typically ultraviolet light, can be obtained.

[0635] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, and BisRS-2 6X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu) The products manufactured by Chemical Industry Co., Ltd. include BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc., but are not limited to these.

[0636] As amino compounds, examples include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylene diamine, 1,3-phenylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, etc., but are not limited to these.

[0637] Furthermore, examples of polyhydroxy polyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but these are not limited to.

[0638] Among these, quinone diazide compounds are preferred, containing phenolic compounds and esters with 4-naphthoquinone diazidesulfonyl groups. This allows for higher sensitivity and resolution to i-ray exposure.

[0639] The content of the quinone diazide compound used in the photosensitive composition is preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is therefore preferred. Furthermore, sensitizers, etc., can be added as needed.

[0640] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound").

[0641] There are no particular limitations on the presence of an oxime sulfonate group in the oxime sulfonate compound, but it is preferred to be an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104) or formula (OS-105).

[0642] [Chemical Formula 30]

[0643]

[0644] In equation (OS-1), X 3 This indicates an alkyl, alkoxy, or halogen atom. The presence of multiple X atoms... 3 In this case, they can be the same or different. The above X 3 The alkyl and alkoxy groups in X may have substituents. As described above, X... 3 The alkyl group in the text is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. As described above, X... 3 The alkoxy group in the form is preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. As described above, X... 3 The halogen atom in the sample is preferably a chlorine atom or a fluorine atom.

[0645] 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 They can be the same or different.

[0646] In equation (OS-1), R 34The symbol represents an alkyl or aryl group, specifically an alkyl group having 1 to 10 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can be substituted with 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 haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloaryl group having 6 to 20 carbon atoms.

[0647] In equation (OS-1), m3 is 3, X 3 Methyl, X 3 The replacement position is adjacent, R 34 Particularly preferred are compounds with straight-chain alkyl groups having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorborneolmethyl, or p-tolyl groups.

[0648] As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 are examples, and these contents are incorporated into this specification.

[0649] [Chemical Formula 31]

[0650]

[0651] In formula (OS-103) to formula (OS-105), R s1 Indicates alkyl, aryl, or heteroaryl, sometimes with multiple Rs. s2 Each R can independently represent a hydrogen atom, alkyl group, aryl group, or halogen atom; sometimes multiple Rs are present. s6 Each of these groups independently represents a halogen atom, alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group, or alkoxysulfonyl group. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6.

[0652] In formula (OS-103) to formula (OS-105), R s1 The alkyl (preferably 1 to 30 carbon atoms), aryl (preferably 6 to 30 carbon atoms), or heteroaryl (preferably 4 to 30 carbon atoms) represented may have known substituents within the range that can achieve the effects of the present invention.

[0653] In formula (OS-103) to formula (OS-105), R s2 Preferably, it is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. Sometimes more than two R atoms are present in the compound.s2 In this configuration, preferably one or two atoms are alkyl, aryl, or halogen atoms, more preferably one atom is alkyl, aryl, or halogen atom, and particularly preferably one atom is alkyl with the remainder being hydrogen atoms. s2 The alkyl or aryl groups represented may have known substituents within the range that allows the effects of the present invention to be obtained.

[0654] In formulas (OS-103), (OS-104), or (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 element is a 5-membered ring or a 6-membered ring.

[0655] In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is 0, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0656] In formula (OS-103) to formula (OS-105), R s6 The alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) may have substituents.

[0657] In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0658] Furthermore, the compound represented by the above formula (OS-103) is particularly preferred to be the 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 preferred to be the compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferred to be the compound represented by the following formula (OS-108) or formula (OS-109).

[0659] [Chemical Formula 32]

[0660]

[0661] In formula (OS-106) to formula (OS-111), R t1 R indicates alkyl, aryl, or heteroaryl. t7 R represents a hydrogen atom or a bromine atom. t8 Represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, halogen atoms, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl groups, R t9 R represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group. t2 It represents a hydrogen atom or a methyl group.

[0662] In formula (OS-106) to formula (OS-111), R t7 It represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

[0663] In formula (OS-106) to formula (OS-111), R t8 The atom 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0664] In formula (OS-106) to formula (OS-111), R t9 It represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom.

[0665] R t2 It represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0666] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be either one or a mixture thereof.

[0667] As specific examples of 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 Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 are examples, and these contents are incorporated into this specification.

[0668] As another preferred manner of oxime sulfonate compounds containing at least one oxime sulfonate group, compounds represented by the following formulas (OS-101) and (OS-102) can be cited.

[0669] [Chemical Formula 33]

[0670]

[0671] In formula (OS-101) or formula (OS-102), R u9 This indicates a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acyl, carbamoyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. More preferably, R. u9 In the form of cyano or aryl, R is further preferred. u9 It can be in the form of cyano, phenyl, or naphthyl.

[0672] In formula (OS-101) or formula (OS-102), R u2a Indicates alkyl or aryl.

[0673] In formula (OS-101) or formula (OS-102), Xu represents -0-, -S-, -NH-, and -NR. u5 -, -CH2-, -CR u6 H- or CR u6 R u7 -, R u5 ~R u7 Each can be represented independently as either alkyl or aryl.

[0674] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these can independently represent a hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, amide, sulfonyl, cyano, or aryl. R u1 ~R u4 The two atoms in the ring can bond together to form a ring. At this point, the ring can undergo ring condensation to form a fused ring with the benzene ring. As R... u1 ~R u4 Preferably, hydrogen atoms, halogen atoms or alkyl groups are used, and R is also preferred. u1 ~R u4 The aryl group is formed by at least two of the molecules bonding with each other. Preferably, R... u1 ~R u4 All of these are hydrogen atoms. The above substituents can also have additional substituents.

[0675] The compound represented by the above formula (OS-101) is more preferably the compound represented by formula (OS-102).

[0676] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be either one of them or a mixture thereof.

[0677] As specific examples of compounds represented by formula (OS-101), compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 are examples, and these contents are incorporated into this specification.

[0678] Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

[0679] [Chemical Formula 34]

[0680]

[0681] Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0682] Furthermore, compounds represented by the following structural formulas can be cited as preferred examples.

[0683] [Chemical Formula 35]

[0684]

[0685] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". The compounds described in Chemistry, No. 1 (1970), etc., are included in this specification. In particular, trihalomethyl-substituted oxazole compounds, S-triazine compounds are preferred examples.

[0686] More preferably, examples include s-triazine derivatives formed by bonding at least one mono, di, or trihalogen-substituted methyl group to an s-triazine ring. Specifically, examples include 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, and 2-n-propyl-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-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, [(2-(p-methoxystyryl)-2,4-butadienyl)-4,6-bis(trichloromethyl)-S-triazine, 2-styryl-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-naphthoxy) Examples of triazines include 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, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0687] Examples of organoborate compounds include Japanese Patent Application Publication No. 62-143044, Japanese Patent Application Publication No. 62-150242, Japanese Patent Application Publication No. 9-188685, Japanese Patent Application Publication No. 9-188686, Japanese Patent Application Publication No. 9-188710, Japanese Patent Application Publication No. 2000-131837, Japanese Patent Application Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Publication No. 2002-116539, and Kunz, Martin, “Rad Tech’98. Proceeding April”. Organoborates described in publications such as "Chicago" (19-22, 1998), organoboron sulfonium complexes or organoboron oxysulfonium complexes described in Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and organoboron sulfonium complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553. The present specification includes, as specific examples, organoboron-phosphorus complexes described in Japanese Patent Application Publication No. 9-188710, organoboron-transition metal coordination complexes such as those in Japanese Patent Application Publication No. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, and these contents are incorporated into this specification.

[0688] Examples of disulfone compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2002-328465, as well as diazonium disulfone compounds.

[0689] Examples of the aforementioned onium salt compounds include, for instance, the diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T.S. Ba et al., Polymer, 21, 423 (1980); the ammonium salts described in U.S. Patent No. 4,069,055 and Japanese Patent Application Publication No. 4-365049; the phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; the phosphonium salts described in European Patent Nos. 104,143, 339,049, and 410,201; the phosphonium salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and the phosphonium salts described in European Patent Nos. 370,693 and 3... The matte salts described in the specifications of U.S. Patent Nos. 90,214, 233,567, 297,443, 297,442, 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, and 3,604,581, and JVCrivello... Selenium salts described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), are included in this specification.

[0690] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III).

[0691] [Chemical Formula 36]

[0692]

[0693] In formula (RI-I), Ar 11The term refers to aryl groups having 1 to 6 substituents and having 20 or fewer carbon atoms. Preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 2 to 12 carbon atoms, alkylamide groups with 1 to 12 carbon atoms of alkyl groups, or arylamide groups with 6 to 20 carbon atoms of aryl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. 11 - The term represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. From a stability perspective, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, or sulfinic acid ion are preferred. In formula (RI-II), Ar... 21 Ar 22 Each of the substituents can independently represent an aryl group having 1 to 6 substituents and a carbon number of 1 to 20. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups with alkyl groups having 1 to 12 carbon atoms each, alkylamide or arylamide groups with alkyl groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 21 - The term represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. Considering stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred. In formula (RI-III), R... 31 R 32 R 33Each group can independently represent an aryl or alkyl, alkenyl, or alkynyl group with 6 to 20 carbon atoms and 1 to 6 substituents. Preferably, from the perspective of reactivity and stability, an aryl group is preferred. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms of each alkyl group, alkylamide or arylamide groups with 1 to 12 carbon atoms of the alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. 31 - The anions with a monovalent charge are halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, thiosulfonic acid ions, and sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

[0694] Specific examples of preferred photoacid-generating agents include the following.

[0695] [Chemical Formula 37]

[0696]

[0697] [Chemical Formula 38]

[0698]

[0699] [Chemical Formula 39]

[0700]

[0701] [Chemical Formula 40]

[0702]

[0703] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the photosensitizing composition, more preferably at 0.5 to 18% by mass, even more preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass.

[0704] Photoacid-generating agents can be used alone or in combination. When multiple agents are used in combination, the total dosage is preferably within the range mentioned above.

[0705] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it simultaneously with a sensitizer.

[0706] <Alkali-generating agents>

[0707] The photosensitive composition may contain an alkali-generating agent. The alkali-generating agent is a compound capable of generating an alkali through physical or chemical action. Preferred alkali-generating agents for the photosensitive composition include thermal alkali-generating agents and photoalkali-generating agents.

[0708] In particular, when the photosensitive composition contains a precursor of a cyclized resin, the photosensitive composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent in the photosensitive composition, such as by heating, the cyclization reaction of the precursor can be promoted, resulting in improved mechanical properties or chemical resistance of the cured product, for example, improved performance as an interlayer insulating film for rewiring layers included in semiconductor packages.

[0709] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include secondary and tertiary amines.

[0710] There are no particular limitations on the alkali generating agent involved in this invention, and known alkali generating agents can be used. Examples of known alkali generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0711] Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3).

[0712] [Chemical Formula 41]

[0713]

[0714] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each can be independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Among them, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0715] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, more preferably at least two rings. The cyclic structure can be any of a monocyclic ring or a fused ring, preferably a monocyclic ring or a fused ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0716] More specifically, Rb 1 and Rb 2 Preferably, the groups are hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). These groups may have substituents within the range that enables the effects of the present invention. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are 4- to 7-membered nitrogen-containing heterocycles. In particular, Rb... 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0717] As Rb 3Examples of suitable carbon atoms include alkyl (preferably 1-24 carbon atoms, more preferably 2-18, even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, even more preferably 6-10), alkenyl (preferably 2-24 carbon atoms, more preferably 2-12, even more preferably 2-6), aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, even more preferably 7-12), arylenyl (preferably 8-24 carbon atoms, more preferably 8-20, even more preferably 8-16), alkoxy (preferably 1-24 carbon atoms, more preferably 2-18, even more preferably 3-12), aryloxy (preferably 6-22 carbon atoms, more preferably 6-18, even more preferably 6-12), or arylalkoxy (preferably 7-23 carbon atoms, more preferably 7-19, even more preferably 7-12). Among these, cycloalkyl (preferably 3-24 carbon atoms, more preferably 3-18, even more preferably 3-12), arylenyl, and arylalkoxy are preferred. Rb 3 Substituents may also be present within the scope of achieving the effects of this invention.

[0718] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below.

[0719] [Chemical Formula 42]

[0720]

[0721] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 The meanings are the same.

[0722] Rb 13 The groups are alkyl (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or aralkyl (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), and may have substituents within the range that enables the effects of the present invention. Rb 13 Preferably, it is an aryl alkyl group.

[0723] Rb 33 and Rb 34Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0724] Rb 35 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), and preferably aryl.

[0725] Furthermore, the compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0726] [Chemical Formula 43]

[0727]

[0728] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 The meanings are the same.

[0729] Rb 15 and Rb 16 The atom is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), an aralkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0730] Rb 17 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), wherein aryl is preferred.

[0731] [Chemical Formula 44]

[0732]

[0733] In formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is three or more. Furthermore, R... N1 and R N2 Each organic group can be represented independently with a valence of 1.

[0734] In this specification, a "linking chain" refers to a chain of atoms that connects two atoms or groups of atoms in the shortest possible way. For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms in the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0735] [Chemical Formula 45]

[0736]

[0737] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-described intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and particularly preferably 4. Specific preferred compounds as base generating agents include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0738] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0739] [Chemical Formula 46]

[0740]

[0741] In equation (N1), R N1 and R N2 R represents a monovalent organic group independently. C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0742] L is a divalent linker, preferably a divalent organogroup. The linker chain length is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0743] In equation (N1), R N1 and R N2 Each organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12) is independently represented by a monovalent organic group, preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with aliphatic hydrocarbon groups being preferred. If R is used as... N1 and R N2 Using aliphatic hydrocarbon groups results in a highly basic base, which is therefore preferred. Furthermore, aliphatic and aromatic hydrocarbon groups can have substituents, and these groups can have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or in the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0744] As a component of R N1 and R N2 Examples of aliphatic hydrocarbon groups include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups relating to combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Straight-chain or branched chain alkyl groups are preferably alkyl groups with 1 to 24 carbon atoms, more preferably alkyl groups with 2 to 18 carbon atoms, and even more preferably alkyl groups with 3 to 12 carbon atoms. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, pentapentyl, tert-pentyl, and isohexyl.

[0745] Cyclic alkyl groups are preferably alkyl groups with 3 to 12 carbon atoms, and more preferably alkyl groups with 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0746] The group relating to the combination of chain alkyl and cyclic alkyl groups is preferably a group with 4 to 24 carbon atoms, more preferably a group with 4 to 18 carbon atoms, and even more preferably a group with 4 to 12 carbon atoms. Examples of groups relating to the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0747] The alkyl group having an oxygen atom in the chain is preferably an alkyl group with 2 to 12 carbon atoms, more preferably an alkyl group with 2 to 6 carbon atoms, and even more preferably an alkyl group with 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0748] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, it is an alkyl group having 5 to 12 carbon atoms. In formulations where close contact with metals (e.g., copper) is important, it is preferred to have a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms.

[0749] R N1 and R N2 They can connect to each other to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, R... N1 and R N2 The formed ring structure can be a monocyclic ring or a fused ring, but a monocyclic ring is preferred. The preferred ring structure is a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazole idine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings being particularly preferred.

[0750] R C1 This indicates a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0751] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0752] Specific examples of protecting groups include chain-like or cyclic alkyl groups, or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl. Specifically, examples of chain-like alkyl groups having oxygen atoms in the chain include alkyloxyalkyl groups, and more specifically, examples include methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP).

[0753] There are no particular restrictions on the divalent linking group constituting L, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents and may also have atoms of any kind other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain is more preferred. A divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain is even more preferred. These groups preferably do not have an oxygen atom.

[0754] The divalent hydrocarbon linking group is preferably a hydrocarbon linking group with 1 to 24 carbon atoms, more preferably a hydrocarbon linking group with 2 to 12 carbon atoms, and even more preferably a hydrocarbon linking group with 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group with 2 to 6 carbon atoms, and even more preferably an aliphatic hydrocarbon group with 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group is preferably an aromatic hydrocarbon group with 6 to 22 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 18 carbon atoms, and even more preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms. The group (e.g., arylalkylene) associated with the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group is preferably a group with 7 to 22 carbon atoms, more preferably a group with 7 to 18 carbon atoms, and even more preferably a group with 7 to 10 carbon atoms.

[0755] As the linking group L, specifically, linear or branched chain alkylene, cyclic alkylene, groups relating to combinations of linear and cyclic alkylene, alkylene having an oxygen atom in the chain, linear or branched chain alkenyl, cyclic alkenyl, arylene, and arylalkylene are preferred.

[0756] The linear or branched alkylene compounds are preferably linear alkylene compounds with 1 to 12 carbon atoms, more preferably linear alkylene compounds with 2 to 6 carbon atoms, and even more preferably linear alkylene compounds with 2 to 4 carbon atoms.

[0757] Cyclic alkylene compounds are preferably cyclic alkylene compounds with 3 to 12 carbon atoms, and more preferably cyclic alkylene compounds with 3 to 6 carbon atoms.

[0758] The groups associated with combinations of chain alkylene and cyclic alkylene are preferably groups with 4 to 24 carbon atoms, more preferably groups with 4 to 12 carbon atoms, and even more preferably groups with 4 to 6 carbon atoms.

[0759] The alkylene group having an oxygen atom in the chain can be chain-like or cyclic, and can be straight-chain or branched. Preferably, the alkylene group having an oxygen atom in the chain is an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms.

[0760] The linear or branched chain-like alkenyl group is preferably an alkenyl group with 2 to 12 carbon atoms, more preferably an alkenyl group with 2 to 6 carbon atoms, and even more preferably an alkenyl group with 2 to 3 carbon atoms. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0761] The cyclic alkenyl group is preferably an alkenyl group with 3 to 12 carbon atoms, more preferably an alkenyl group with 3 to 6 carbon atoms. The number of C=C bonds in the cyclic alkenyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0762] The arylene group is preferably an arylene group with 6 to 22 carbon atoms, more preferably an arylene group with 6 to 18 carbon atoms, and even more preferably an arylene group with 6 to 10 carbon atoms.

[0763] The arylene alkylene is preferably an arylene alkylene with 7 to 23 carbon atoms, more preferably an arylene alkylene with 7 to 19 carbon atoms, and even more preferably an arylene alkylene with 7 to 11 carbon atoms.

[0764] Preferably, the alkylene chain, alkylene ring, alkylene ring having an oxygen atom in the chain, alkenyl chain, aryl chain, aryl chain, and alkylene ring are used; more preferably, 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and oxyethylene (especially 1,2-ethoxy-1,2-ethylene).

[0765] Examples of alkali-generating agents can be given below, but the present invention is not limited thereto.

[0766] [Chemical Formula 47]

[0767]

[0768] The molecular weight of the nonionic hot alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0769] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0770] Specific examples of ammonium salts include the following compounds, but the invention is not limited to these.

[0771] [Chemical Formula 48]

[0772]

[0773] Specific examples of imine salts include the following compounds, but the invention is not limited to these.

[0774] [Chemical Formula 49]

[0775]

[0776] When the photosensitive composition contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of the resin in the photosensitive composition. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, but can be 5 parts by weight or less, or 4 parts by weight or less.

[0777] One or more alkali-generating agents can be used. When using two or more, the total dosage is preferably within the range described above.

[0778] Solvent

[0779] The photosensitive composition preferably contains a solvent.

[0780] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0781] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate). Esters, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0782] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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 dimethyl 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, and dipropylene glycol dimethyl ether.

[0783] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone.

[0784] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred hydrocarbons.

[0785] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0786] Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0787] Examples of preferred urea types include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0788] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene 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, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0789] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0790] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucanone, and dihydroglucanone, or a mixed solvent consisting of two or more of these solvents, is preferred. Particularly preferred is the simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate.

[0791] From a coating properties perspective, it is preferable to set the solvent content to an amount that is 5 to 80% by mass of the total solids concentration of the photosensitive composition, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired film thickness and coating method.

[0792] The photosensitive composition may contain only one solvent or two or more solvents. When it contains two or more solvents, their total amount is preferably within the range described above.

[0793] <Metal Adhesion Modifier>

[0794] The photosensitive composition preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0795] Silane coupling agent

[0796] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, and these contents are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Moreover, the following compounds are preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0797] [Chemical Formula 50]

[0798]

[0799] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tri-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0800] [Aluminum-based adhesive additives]

[0801] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropoxide aluminum ethyl acetoacetate.

[0802] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated into this specification.

[0803] The content of the metal adhesion modifier relative to the mass of resin A100 is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.01 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier can be only one type or two or more types. When using two or more types, their total content is preferably within the above range.

[0804] <Migration Inhibitor>

[0805] The photosensitizing composition preferably further comprises a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

[0806] There are no particular limitations on the migration inhibitors, but compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acylhydrazine derivative compounds are preferred. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0807] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0808] Other migration inhibitors may be used, including the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, and these contents are incorporated into this specification.

[0809] The following compounds can be cited as specific examples of migration inhibitors.

[0810] [Chemical Formula 51]

[0811]

[0812] When the photosensitive composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass relative to the total solid content of the photosensitive composition, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0813] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range mentioned above.

[0814] <Polymerization inhibitors>

[0815] The photosensitizing composition preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0816] Specific compounds used as polymerization inhibitors include, for example, p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N- Sulfopropylamine, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6 6-Tetramethylpiperidine 1-oxy radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-pyrrolidine, copper(II) dibutyldithiocarbamate, nitrobenzene, aluminum N-nitroso-N-phenylhydroxylamine, ammonium N-nitroso-N-phenylhydroxylamine, Taobn (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide), etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Patent Publication No. 2015 / 125469 can also be used, and this content is incorporated into this specification.

[0817] When the photosensitive composition contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0818] The polymerization inhibitor can be one type or two or more types. When there are two or more polymerization inhibitors, their total number is preferably within the range described above.

[0819] Acid scavenger

[0820] To reduce performance changes caused by the passage of time from exposure to heating, the photosensitizing composition preferably contains an acid scavenger. The acid scavenger is a compound that can capture acid-generating substances by being present in the system, and is preferably a compound with low acidity and high pKa. As an acid scavenger, compounds having an amino group are preferred, more preferably primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc., further preferably primary amines, secondary amines, tertiary amines, and ammonium salts, and particularly preferably secondary amines, tertiary amines, and ammonium salts.

[0821] Examples of preferred acid scavengers include compounds having imidazole, diazabicyclic, ononium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and / or ether bonds; and aniline derivatives having hydroxyl and / or ether bonds. In the case of an ononium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, monazine, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than that produced by the acid generator.

[0822] Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers with a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers with a onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, benzoylmethylsulfonium hydroxide, sulfonium hydroxides with 2-oxoalkyl groups, specifically triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)sulfonium hydroxide, benzoylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers with a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and / or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tri(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and / or ether bonds include N,N-bis(hydroxyethyl)aniline.

[0823] Specific examples of preferred acid scavenging agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N- Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0824] These acid scavengers can be used alone or in combination of two or more.

[0825] The compositions involved in this invention may or may not contain an acid scavenger, but when they do contain an acid scavenger, the content of the acid scavenger is based on the total solid content of the composition, typically 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

[0826] The preferred ratio of acid generator to acid scavenger is an acid generator / acid scavenger molar ratio of 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, a molar ratio of 2.5 or higher is preferred, and from the viewpoint of suppressing the decrease in resolution caused by the thickening of the pattern over time from exposure to heat treatment, a ratio of 300 or lower is preferred. An acid generator / acid scavenger molar ratio is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0827] <Other Additives>

[0828] The photosensitive composition can be formulated with various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymers, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as needed to achieve the effects of the present invention. By appropriately containing these components, the physical properties of the film can be adjusted. Regarding these components, reference can be made to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812) and paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein by reference. When these additives are incorporated, it is preferable that their total amount is set to 3% by mass or less of the solid components of the photosensitive composition.

[0829] [surfactants]

[0830] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0831] By including a surfactant in the photosensitive composition, the liquid properties (especially flowability) during preparation as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when forming a film using a coating liquid containing a surfactant-containing composition, the interfacial tension between the coated surface and the coating liquid is reduced, improving the wettability of the coated surface and thus enhancing the coating properties. Therefore, it is more preferable to form a film with a uniform thickness and minimal thickness non-uniformity.

[0832] Examples of fluorinated surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASolutions Inc.), etc. Fluorinated surfactants may also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, and these contents are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0833] Fluorinated surfactants can also preferably use fluorinated polymers comprising 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) alkeneoxy groups (preferably ethoxy or propyleneoxy groups). Examples of the following compounds as fluorinated surfactants used in this invention are also provided.

[0834] [Chemical Formula 52]

[0835]

[0836] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0837] Fluorinated surfactants can also be used to treat fluoropolymers with vinyl unsaturated groups on their side chains. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

[0838] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniformity of coating thickness or liquid saving, and also have good solubility in the composition.

[0839] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0840] Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD.).

[0841] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters. As commercially available products, examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), 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 Co., LTD.), etc.

[0842] As cationic surfactants, examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0843] As anionic surfactants, examples include WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0844] Surfactants can be used in single-agent or in combination of two or more.

[0845] The surfactant content is preferably 0.001 to 2.0% by mass relative to the total solids content of the composition, more preferably 0.005 to 1.0% by mass.

[0846] [Higher fatty acid derivatives]

[0847] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the photosensitive composition, so that they are unevenly present on the surface of the photosensitive composition during the drying process after coating.

[0848] Furthermore, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 may also be used for higher fatty acid derivatives, and this content is incorporated into this specification.

[0849] When the photosensitive composition contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solids content of the photosensitive composition. There may be only one type of higher fatty acid derivative or two or more types. When there are two or more higher fatty acid derivatives, their total content is preferably within the above range.

[0850] [Thermal polymerization initiator]

[0851] The photosensitive composition may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of polymerizable compounds. By adding a thermal free radical polymerization initiator, polymerization reactions of resins and polymerizable compounds can also occur, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization through heat, and can sometimes be added as thermal polymerization initiators.

[0852] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as thermal free radical polymerization initiators, and this content is incorporated into this specification.

[0853] When a thermal polymerization initiator is included, its content relative to the total solids content of the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may be one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0854] [Inorganic particles]

[0855] The photosensitive composition may contain inorganic particles. Specifically, these inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0856] The average particle size of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0857] The average particle size mentioned above is the primary particle size and the volume average particle size. The volume average particle size can be determined by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

[0858] In cases where the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0859] [Ultraviolet absorber]

[0860] The photosensitizing composition may contain a UV absorber. As a UV absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other UV absorbers can be used.

[0861] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0862] Examples of acrylonitrile-based UV absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0863] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more.

[0864] The photosensitive composition may or may not contain a UV absorber, but when it does contain a UV absorber, the content of the UV absorber is preferably 0.001% by mass or more and 1% by mass or less relative to the total solid content of the photosensitive composition, more preferably 0.01% by mass or more and 0.1% by mass or less.

[0865] [Organotitanium compounds]

[0866] The photosensitive composition of this embodiment may contain an organotitanium compound. Because the photosensitive composition contains an organotitanium compound, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0867] As usable organotitanium compounds, examples include compounds in which the organic group is bonded to titanium atoms via covalent or ionic bonds.

[0868] Specific examples of organotitanium compounds are shown in I) to VII) below:

[0869] I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are preferred because they exhibit excellent storage stability of the photosensitive composition and can achieve good cured patterns. Specific examples include diisopropanol bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropanol bis(2,4-pentanedione) titanium, diisopropanol bis(tetramethylheptanedione) titanium, and diisopropanol bis(ethyl acetoacetate) titanium.

[0870] II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenyl oxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

[0871] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0872] IV) Monoalkoxy titanium compounds: such as titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc.

[0873] V) Titanium oxide compounds: such as titanium dioxide bis(pentanedione), titanium dioxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.

[0874] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0875] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0876] Among these, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) diacetic titanium compound is preferred as the organotitanium compound. In particular, diisopropanol bis(ethyl acetoacetate) titanium, tetra(n-butanol) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0877] When an organotitanium compound is incorporated, its amount relative to the mass of resin A100 is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass. When the amount is 0.05 parts by mass or more, the cured pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount is 10 parts by mass or less, the composition exhibits better storage stability.

[0878] [Antioxidants]

[0879] The photosensitive composition may contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Compounds having substituents at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, the antioxidant is also preferably a compound having both a phenolic group and a phosphite group within the same molecule. Furthermore, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, and this content is incorporated into this specification. Additionally, the photosensitive composition may contain potential antioxidants as needed. As potential antioxidants, compounds in which the site of antioxidant function is protected by a protecting group can be cited, and compounds that exert their antioxidant function by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst to remove the protecting group can be cited as potential antioxidants. Compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 can be cited as potential antioxidants, and these contents are included in this specification. Commercially available products as potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0880] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0881] [Chemical Formula 53]

[0882]

[0883] In general formula (3), R 5 R represents an alkyl group having 2 or more hydrogen atoms or carbon atoms (preferably 2 to 10 carbon atoms). 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 It refers to an alkylene group with 2 or more carbon atoms (preferably 2 to 10 carbon atoms) or an organogroup with a valence of 1 to 4 containing at least one of an oxygen atom and a nitrogen atom. k represents an integer from 1 to 4.

[0884] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0885] It can act on both resin and metal materials simultaneously, therefore, it is more preferable that k is an integer from 2 to 4. As R 7 Examples of suitable groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and substituents may also be present. From the viewpoint of solubility in the developer and metal adhesion, alkyl ether groups and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion during metal complex formation, -NH- is more preferred.

[0886] Regarding the compounds represented by general formula (3), the following examples can be given, but are not limited to the following structures.

[0887] [Chemical Formula 54]

[0888]

[0889] [Chemical Formula 55]

[0890]

[0891] [Chemical Formula 56]

[0892]

[0893] [Chemical Formula 57]

[0894]

[0895] The amount of antioxidant added is preferably 0.1 to 10 parts by weight relative to the resin, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain effects that improve elongation properties or adhesion to metallic materials, even under high temperature and high humidity environments. Furthermore, by setting the amount added to 10 parts by weight or less, the sensitivity of the photosensitizing composition can be improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount of these antioxidants is preferably within the above-mentioned range.

[0896] [Anticoagulant]

[0897] The photosensitive composition of this embodiment may contain an anti-coagulation agent as needed. Examples of anti-coagulation agents include sodium polyacrylate.

[0898] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[0899] The photosensitive composition may or may not contain an anti-agglomerate, but when it does contain an anti-agglomerate, the content of the anti-agglomerate relative to the total solids content of the photosensitive composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less.

[0900] [Phenolic compounds]

[0901] The photosensitive composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

[0902] In this invention, phenolic compounds can be used alone or in combination of two or more.

[0903] The photosensitive composition may or may not contain phenolic compounds, but when it does contain phenolic compounds, the content of phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less relative to the total solid content of the photosensitive composition, more preferably 0.02% by mass or more and 20% by mass or less.

[0904] [Other polymers]

[0905] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0906] In this invention, other polymer compounds can be used alone or in combination of two or more.

[0907] The photosensitive composition may or may not contain other polymeric compounds, but when it does contain other polymeric compounds, the content of other polymeric compounds is preferably 0.01% by mass or more and 30% by mass or less relative to the total solid content of the photosensitive composition, more preferably 0.02% by mass or more and 20% by mass or less.

[0908] <Characteristics of Photosensitive Compositions>

[0909] The viscosity of the photosensitive composition can be adjusted by the concentration of its solid components. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For 1,000 mm... 2 If the thickness is above / s, then it is easy to coat with the film thickness required for the interlayer insulation film used as a rewiring layer, for example, if it is 12,000 mm. 2 When the speed is below a certain value, a coating with excellent surface shape can be obtained.

[0910] <Limitations on the substances contained in photosensitive compositions>

[0911] The water content of the photosensitive composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. As long as it is less than 2.0%, the storage stability of the photosensitive composition is improved.

[0912] Methods for maintaining moisture content include adjusting the humidity in storage conditions and reducing the porosity of the storage container.

[0913] From an insulating point of view, the metal content of the photosensitizing composition is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds with metals. When multiple metals are included, the total amount of these metals is preferably within the range described above.

[0914] Furthermore, as a method to reduce metal impurities accidentally included in the photosensitive composition, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the photosensitive composition; filtering the raw materials constituting the photosensitive composition with a filter; lining the device with polytetrafluoroethylene or the like to carry out distillation under conditions that suppress contamination as much as possible.

[0915] If the photosensitive composition is considered for use as a semiconductor material, from the viewpoint of wiring corrosion, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of this, the content of substances existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is preferably within the above-mentioned ranges.

[0916] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0917] As a container for the photosensitive composition, conventionally known containers can be used. Furthermore, to prevent impurities from contaminating the raw materials or the photosensitive composition, multi-layered bottles with an inner wall composed of six layers of six different resins, or bottles with a seven-layer structure formed from the six resins, are preferred as containers. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0918] <Preparation of Photosensitive Compositions>

[0919] The photosensitive composition can be prepared by mixing the above-mentioned components. There is no particular limitation on the mixing method, and it can be carried out by conventionally known methods.

[0920] Mixing can be achieved through methods such as mixing based on stirring blades, mixing based on ball mills, and mixing by rotating the tank itself.

[0921] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0922] Furthermore, to remove foreign matter such as dust or particles from the photosensitive composition, filtration using a filter is preferable. Regarding the filter pore size, for example, a pore size of 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter that has been pre-cleaned with an organic solvent. Multiple filters can be used in series or in parallel during the filtration process. When using multiple filters, filters with different pore sizes or materials can be used in combination. For example, a connection method can be used where a 1 μm pore size HDPE filter is used as the first stage and a 0.2 μm pore size HDPE filter is used as the second stage, connected in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, cyclic filtration can be used. Filtration can also be performed after pressurization. When pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0923] In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0924] Furthermore, after filtration using a filter, a process can be performed whereby the photosensitive composition filled in the bottle is placed under reduced pressure and then degassed.

[0925] Example

[0926] The present invention will be described in more detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are based on mass.

[0927] <Synthetic Example: Synthesis of Polymer P-1>

[0928] Under a dry nitrogen stream, 13.96 g (0.045 mol) of 4,4'-oxophthalic dianhydride (ODPA, hereinafter referred to as NMP) was dissolved in 100 g of NMP (N-methyl-2-pyrrolidone). 1.09 g (0.010 mol) of MAP (hereinafter referred to as NMP) and 20 g of NMP were then added. Subsequently, 19.95 g (0.033 mol) of HFHA (hereinafter referred to as NMP), 6.00 g (0.010 mol) of Jeffamine ED600 (registered trademark), 0.62 g (0.003 mol) of SiDA (hereinafter referred to as NMP) and 20 g of NMP were added, and the mixture was reacted at 60 °C for 1 hour, followed by stirring at 180 °C for 4 hours. After stirring, the solution was added to 2 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using a vacuum dryer at 50 °C for 72 hours to obtain polymer P-1 powder.

[0929] [Chemical Formula 58]

[0930]

[0931] <Synthetic Example: Synthesis of Polymer P-2>

[0932] 60 g of N-methylpyrrolidone and 13.92 g (38 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane were added to a flask equipped with a stirrer and thermometer and stirred until dissolved. Then, while maintaining the temperature at 0–5 °C, 7.48 g (28 mmol) of dodecanedioyl dichloride and 3.56 g (12 mmol) of 4,4'-diphenyl ether dicarboxylate chloride were added dropwise over 10 minutes. The mixture was then returned to room temperature (25 °C) and stirred for 3 hours. The solution was then added to 3 liters of water, and the precipitate was recovered. After washing three times with pure water, the solution was subjected to reduced pressure to obtain polyhydroxyamide (hereinafter referred to as polymer P-2). Polymer P-2 has a weight-average molecular weight of 41,800 and a dispersion of 2.0.

[0933] Polymer P-2 is a resin with the following structure. In the following description, x:y represents the molar ratio of each repeating unit.

[0934] [Chemical Formula 59]

[0935]

[0936] <Synthetic Example: Synthesis of Polymer P-3>

[0937] To a solution obtained by dissolving 23.5 g of 4,4'-oxophthalic dianhydride (ODPA) in 190 g of 3-methoxy-N,N-dimethylpropionamide, a solution obtained by dissolving 13 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) in 75 g of 3-methoxy-N,N-dimethylpropionamide was added dropwise, and the mixture was stirred at 30 °C for 2 hours to obtain polyamic acid.

[0938] 37 g of trifluoroacetic anhydride was added to the mixture at a temperature below 40°C, and the mixture was stirred at 45°C for 3 hours. Then, 25.5 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was stirred at 40°C for 10 hours. The reaction mixture was then added dropwise to distilled water three times. The precipitate was collected by filtration and dried under reduced pressure to obtain the polyimide precursor.

[0939] The weight-average molecular weight, number-average molecular weight, and dispersity were determined using gel permeation chromatography (GPC) under the following conditions, converted from standard polystyrene. The polymer P-3 had a weight-average molecular weight of 20,000 and a dispersity of 1.74.

[0940] Polymer P-3 is a resin with the following structure.

[0941] [Chemical Formula 60]

[0942]

[0943] <Synthetic Example: Synthesis of Polymer P-4>

[0944] 20.0 g (64.5 mmol) of 4,4'-oxophthalic anhydride (dried at 140 °C for 12 h), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed. The mixture was then stirred at 60 °C for 18 h to produce a diester of 4,4'-oxophthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -5 °C, and 16.12 g (135.5 mmol) of SOCl2 was added over 2 h while maintaining the temperature at -5 ± 2 °C. Next, a solution obtained by dissolving 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0 °C and added dropwise to the reaction mixture over 2 hours. After reacting the reaction mixture at 0 °C for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature for 1 hour.

[0945] Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried at 45°C for 2 days under reduced pressure to obtain polymer P-4. The weight-average molecular weight of polymer P-4 (polyimide precursor) was 18,000.

[0946] Polymer P-4 is a resin with the following structure.

[0947] [Chemical Formula 61]

[0948]

[0949] <Synthetic Example: Synthesis of Polymer P-5>

[0950] 7.76 g (25 mmol) of 4,4'-oxophthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride were added to a reaction vessel, along with 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone. 7.91 g of pyridine was added while stirring at room temperature to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was cooled to room temperature and allowed to stand for 16 hours.

[0951] Next, under ice-cooled conditions, a solution obtained by dissolving 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring.

[0952] Then, after stirring at room temperature for 2 hours, 3 ml of ethanol was added and stirring was continued for 1 hour. Next, 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

[0953] The obtained reaction solution was added to 3 liters of ethanol, resulting in a precipitate of crude polymer. The crude polymer was filtered off and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3 liters of water to precipitate the polymer, and the precipitate was filtered off and then vacuum dried to obtain powdered polymer P-5.

[0954] The weight-average molecular weight (Mw) of the polymer was determined to be 23,000.

[0955] Polymer P-5 is a resin with the following structure. The subscripts in parentheses indicate the molar ratio of each repeating unit.

[0956] [Chemical Formula 62]

[0957]

[0958] <Examples and Comparative Examples>

[0959] Compositions 1 to 9 were obtained by mixing the ingredients listed in the table below.

[0960] The values ​​recorded in the table are expressed in "parts by mass" to indicate the content of each component.

[0961] The obtained composition was pressure filtered through a polytetrafluoroethylene filter with a pore size of 0.8 μm.

[0962] Furthermore, in the table, a "-" indicates that the corresponding ingredient is not present.

[0963] [Table 1]

[0964]

[0965] The detailed information of each component recorded in the table is as follows.

[0966] [Resin]

[0967] • P-1 to P-5: P-1 to P-5 synthesized as described above

[0968] [Polymerizing compounds]

[0969] • B-1: SR-209 (manufactured by Sartomer)

[0970] ·B-2: NIKALAC MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

[0971] ·B-3: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.)

[0972] •B-4: Triethylene glycol dimethacrylate

[0973] ·B-5: Made by Shin-Nakamura Chemical Co., Ltd., A-TMMT

[0974] [Photosensitizer]

[0975] • C-1: Irgacure OXE-01 (manufactured by BASF)

[0976] • C-2: Irgacure 784 (manufactured by BASF)

[0977] • C-3: Compounds with the following structures. 2∶1 indicates the molar ratio of each structure.

[0978] [Chemical Formula 63]

[0979]

[0980] [Metal adhesion modifier]

[0981] D-1: γ-Ureapropyltriethylsilane

[0982] D-2: N-[3-(triethoxysilyl)propyl]maleic acid (CAS. 33525-68-7)

[0983] [Migration Inhibitor]

[0984] E-1: (5-Aminotetrazole)

[0985] E-2: Tetrazol

[0986] [Polymerization inhibitor]

[0987] F-1: 2MeHQ (methoxyhydroquinone)

[0988] F-2: Taobn(1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide)

[0989] F-3: PBQ (p-benzoquinone)

[0990] F-4: MEHQ (4-methoxyphenol)

[0991] [Alkali-generating agent]

[0992] ·G-1: (1-[4-(2-hydroxyethyl)-1-piperidinyl)]-3-(2-hydroxyphenyl)-1-propanone)

[0993] • G-2: (A compound with the following structure)

[0994] [Chemical Formula 64]

[0995]

[0996] 〔additive〕

[0997] H-1: Compounds with the following structure

[0998] H-2: Compounds with the following structure

[0999] H-3: 7-Diethylamino-4-methylcoumarin

[1000] [Chemical Formula 65]

[1001]

[1002] Solvent

[1003] • I-1: GBL (γ-butyrolactone)

[1004] • I-2: DMSO (dimethyl sulfoxide)

[1005] • I-3: MDM (diethylene glycol dimethyl ether)

[1006] • I-4: IPA (Isopropanol)

[1007] • I-5: EL (ethyl lactate)

[1008] • I-6: NMP (N-methyl-2-pyrroli...

Claims

1. A method for manufacturing a cured material, comprising: The film forming process involves applying a photosensitive composition onto a substrate to form a photosensitive film; The exposure process selectively exposes the photosensitive film; The developing process involves using a developing solution to develop the exposed photosensitive film to form a pattern. and The electromagnetic wave irradiation process involves irradiating the pattern obtained through the development process with electromagnetic waves of wavelengths greater than 780 nm and less than 5 μm. The photosensitive composition comprises at least one resin selected from polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

2. The method for manufacturing a cured product according to claim 1, wherein, The photosensitive composition comprises a polymeric compound.

3. The method for manufacturing a cured product according to claim 1, wherein, The photosensitive composition contains an organometallic complex as a polymerization initiator.

4. The method for manufacturing a cured product according to claim 1, wherein, The glass transition temperature of the obtained cured product exceeds 200℃.

5. The method for manufacturing a cured product according to claim 1, wherein, The temperature of the pattern in the electromagnetic wave irradiation process is below 300°C.

6. The method for manufacturing a cured product according to claim 1, wherein, In the electromagnetic wave irradiation process, the total time for irradiating the pattern with electromagnetic waves is less than 60 minutes.

7. The method for manufacturing a cured product according to claim 1, wherein, The electromagnetic irradiation process is carried out in an inert gas atmosphere.

8. The method for manufacturing a cured product according to claim 1, wherein, The electromagnetic irradiation process is carried out in an environment with an oxygen concentration of less than 1000 ppm.

9. The method for manufacturing a cured product according to claim 1, wherein, The thickness of the photosensitive film is 1 μm or more.

10. The method for manufacturing a cured product according to claim 1, wherein, The substrate is a substrate with metal wiring on the surface on which the photosensitive film is formed.

11. The method for manufacturing a cured product according to claim 1, wherein, The photosensitive composition contains a photopolymerization initiator or a photoacid generator.

12. A method for manufacturing a laminate, comprising repeating the steps of the method for manufacturing a cured material according to claim 1 multiple times.

13. The method for manufacturing a laminate according to claim 12, further comprising a metal layer forming step of forming a metal layer on a layer formed from the cured material during the multiple-performation process of manufacturing the cured material.

14. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material according to any one of claims 1 to 11 or the method for manufacturing a laminate according to claim 12 or 13.

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