TW202212992A - Cured product production method, laminate production method, and semiconductor device production method - Google Patents

Abstract

Provided are a cured product production method whereby a cured product having excellent breaking elongation and chemical resistance is obtained, a laminate production method including said cured product production method, and a semiconductor device production method including said cured product production method or said laminate production method. The cured product production method, the laminate production method including the cured product production method, and the semiconductor device production method including the cured product production method or the laminate production method each comprise: a film formation step for forming a photosensitive film by applying a photosensitive composition onto a substrate; an exposure step for selectively exposing the photosensitive film; a development step for using a developing solution to develop the photosensitive film after the exposure and form a pattern; and electromagnetic wave irradiation step for irradiating the pattern obtained in the development step with electromagnetic waves having a frequency of 780 nm to 5 [mu]m.

Description

Manufacturing method of cured product, manufacturing method of laminated body, and manufacturing method of semiconductor element

The present invention relates to a method for producing a cured product, a method for producing a laminate, and a method for producing a semiconductor element.

Resins such as polyimide, polybenzoxazole, and polyimide imide are suitable for various applications because they are excellent in heat resistance, insulating properties, and the like. The above-mentioned application is not particularly limited, but if a semiconductor element for actual mounting is used as an example, a pattern containing these resins may be used as a material for an insulating film or a sealing material, or a protective film. Moreover, the pattern containing these resins can also be used as a base film, a coverlay film, etc. of a flexible substrate.

For example, in the above applications, resins such as polyimide, polybenzoxazole or polyimide It is used in the form of a photosensitive composition of curable resin such as resin. Such a photosensitive composition is applied to a substrate by, for example, coating, and thereafter, exposure, development, modification, etc. are carried out as necessary, whereby a polyimide precursor and a polybenzoxazole precursor can be prepared. , a cured product such as a polyamide imide precursor is formed on the substrate. The photosensitive composition can be applied by a known coating method or the like, and can form a fine pattern, a pattern of a complicated shape, or the like by development. Therefore, it can be said that the degree of freedom in the design of the cured product is high, and the suitability for manufacture is excellent. In addition to the high performance of resins such as polyimide, polybenzoxazole, polyimide imide, etc., from the viewpoint of excellent suitability for such production, it is increasingly expected that the use of resins containing curable resins Industrial application and development of the manufacturing method of the cured product of the photosensitive composition.

For example, Patent Document 1 describes a method including heating a polyimide fiber at a temperature in the range of the first temperature to the second temperature for 5 seconds to 5 minutes in order to form the polyimide fiber. wherein the first temperature is the imidization temperature of the polyimide, and the second temperature is the decomposition temperature of the polyimide. Patent Document 2 describes a resin composition comprising a polyimide precursor containing a specific structural unit and a solvent, wherein the solvent is an amide-based solvent and a non-amide having a boiling point of 160°C or higher It is a mixture of solvents and contains the specific compound in an amount of more than 0 ppm and 1200 ppm or less based on the mass of the resin composition.

[Patent Document 1] Japanese Patent Publication No. 2013-539824 [Patent Document 2] Japanese Patent Laid-Open No. 2019-203120

In a conventional method for producing a cured product using a photosensitive composition containing a curable resin such as a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor, it is required to improve the obtained The elongation at break of the cured product and the chemical resistance of the pattern formed by the cured product are improved.

An object of the present invention is to provide a method for producing a cured product that can obtain a cured product excellent in elongation at break and chemical resistance, a method for producing a laminate including the method for producing the above-mentioned cured product, and a method for producing the above-mentioned cured product or The manufacturing method of the semiconductor element which concerns on the manufacturing method of the said laminated body.

Examples of typical embodiments of the present invention are shown below. <1> A method for producing a cured product, comprising: The film forming step is to apply the photosensitive composition to the substrate to form a photosensitive film; an exposure step of selectively exposing the photosensitive film; In the developing step, a developing solution is used to develop the exposed photosensitive film to form a pattern; and The electromagnetic wave irradiation process irradiates the pattern obtained by the said developing process with the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less. <2> The method for producing a cured product according to <1>, wherein the photosensitive composition contains a material selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor. , at least one resin in the group of epoxy resin and phenol resin. <3> The method for producing a cured product according to <1> or <2>, wherein the photosensitive composition contains a material selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide amide At least one resin in the group of imine precursors. <4> The method for producing a cured product according to any one of <1> to <3>, wherein the photosensitive composition contains a polymerizable compound. <5> The method for producing a cured product according to any one of <1> to <4>, wherein the photosensitive composition contains an organometallic complex as a polymerization initiator. <6> The method for producing a cured product according to any one of <1> to <5>, wherein the glass transition temperature of the obtained cured product exceeds 200°C. <7> The method for producing a cured product according to any one of <1> to <6>, wherein the temperature of the pattern in the electromagnetic wave irradiation step is 300° C. or lower. <8> The method for producing a cured product according to any one of <1> to <7>, wherein, in the electromagnetic wave irradiation step, the total time for irradiating the pattern with the electromagnetic wave is 60 minutes or less. <9> The method for producing a cured product according to any one of <1> to <8>, wherein the electromagnetic wave irradiation step is performed in an inert gas atmosphere. <10> The method for producing a cured product according to any one of <1> to <9>, wherein the electromagnetic wave irradiation step is performed in an environment with an oxygen concentration of 1000 ppm or less. <11> The method for producing a cured product according to any one of <1> to <10>, wherein the photosensitive film has a thickness of 1 μm or more. <12> The method for producing a cured product according to any one of <1> to <11>, wherein the base material is a base material provided with metal wiring on the surface on which the photosensitive film is formed. <13> The method for producing a cured product according to any one of <1> to <12>, wherein the photosensitive composition contains a photopolymerization initiator or a photoacid generator. <14> A method for producing a layered body comprising repeating the step of repeating the method for producing a cured product according to any one of <1> to <13>. <15> The method for producing a layered product according to <14>, further comprising a metal layer forming step of forming a metal layer on the layer formed of the hardened product during the method for producing a hardened product performed a plurality of times. <16> A method for producing a semiconductor element, comprising the method for producing a cured product according to any one of <1> to <13>, or the method for producing a laminate according to <14> or <15>. [Inventive effect]

According to the present invention, there are provided a method for producing a cured product that can obtain a cured product excellent in elongation at break and chemical resistance, a method for producing a layered product including the method for producing the above-described cured product, and a method for producing the above-described cured product or the above-mentioned laminate A method of manufacturing a semiconductor device.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. With regard to the labels of groups (atomic groups) in this specification, the labels of unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) 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). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) are connected in series and used for control, and obtained. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the reference layer among the plurality of layers concerned. That is, a third layer or a third element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise stated, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

(Manufacturing method of hardened product) The manufacturing method of the cured product of the present invention includes: a film forming step of applying a photosensitive composition to a substrate to form a photosensitive film; an exposure step of selectively exposing the photosensitive film; The exposed photosensitive film is developed to form a pattern; and an electromagnetic wave irradiation step irradiates an electromagnetic wave having a wavelength of 780 nm or more and 5 μm or less on the pattern obtained by the above-mentioned developing process. According to the method for producing a cured product of the present invention, a cured product excellent in elongation at break and chemical resistance can be obtained. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.

The manufacturing method of the hardened|cured material of this invention includes the electromagnetic wave irradiation process which irradiates the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less to the pattern obtained by the said developing process. The photosensitive film is heated by this electromagnetic wave irradiation step. With regard to the heating based on the above-mentioned electromagnetic wave irradiation step, it is considered that compared with the heating using a box oven, a hot plate, etc. which have been used previously, it proceeds very quickly, and in a state where the photosensitive film is nearly uniform (for example, in a state where the photosensitive film is made of Heating is performed in a state with little heating unevenness due to the position. Therefore, it is presumed that, for example, curing of the curable resin contained in the photosensitive film (for example, cyclization of a polyimide precursor, polymerization of an epoxy resin, etc.), crosslinking of a polymerizable compound, and the like proceed rapidly, and curing degree, crosslinking density, etc. are increased, so that a cured product excellent in chemical resistance can be obtained. Moreover, when the photosensitive film contains a curable resin, it is presumed that the degree of cyclization of the curable resin becomes high as described above, so that a cured product excellent in elongation at break can be obtained. In particular, when the photosensitive film contains a curable resin and a polymerizable compound, the heating rate is slow when heated by a conventional oven oven or the like. Hardening of the curable resin is performed. In this case, it is considered that the degree of freedom of structural change of the curable resin decreases due to the presence of the crosslinked polymerizable compound, and the degree of hardening of the curable resin may decrease. In the method for producing the cured product of the present invention, it is presumed that the heating rate is very fast due to the heating by the electromagnetic wave irradiation step, and the curing of the curable resin can proceed when the degree of progress of the crosslinking of the polymerizable compound is low. The degree of hardening of the resin becomes high, and the elongation at break is excellent.

Among them, Patent Documents 1 to 2 do not describe a method for producing a cured product including the above-mentioned film forming step, exposure step, development step, and electromagnetic wave irradiation step. Hereinafter, the manufacturing method of the hardened|cured material of this invention is demonstrated in detail.

<Film formation step> The manufacturing method of the hardened|cured material of this invention includes the film formation process of applying a photosensitive composition to a base material, and forming a photosensitive film. Details of the photosensitive composition used in the film forming step will be described later.

[Substrate] The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

Moreover, when forming a photosensitive film by applying a photosensitive composition to the surface of a resin layer (for example, the layer formed of hardened|cured material) or the surface of a metal layer, a resin layer or a metal layer becomes a base material. Moreover, it is also preferable that the base material is provided with metal wiring on the surface on which the photosensitive film is formed. In the above-mentioned aspect, as the material of the base material, the above-mentioned semiconductor production base material is preferable. In addition, the metal wiring in the above aspect can be exemplified by copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and wiring based on alloys containing these metals, and wiring based on copper, aluminum and containing the Wiring of alloys of the same metals is more preferable, and wiring based on alloys containing copper or copper is further preferable.

As a method for applying the photosensitive composition to a substrate, coating is preferable.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive film, the spin coating method, the slit coating method, the spray method or the inkjet method is more preferable, and from the viewpoint of the uniformity of the thickness of the photosensitive film and the viewpoint of productivity, The spin coating method and the slit coating method are preferable. By adjusting the solid content concentration and coating conditions of the photosensitive composition according to the method, a photosensitive film of a desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . Moreover, the process of removing the excess photosensitive film in the edge part of a base material can be performed. Examples of such a step include edge bead rinse (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step can also be adopted, in which, before the photosensitive composition is coated on the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the photosensitive composition is applied. .

The film thickness of the photosensitive film (the film thickness after the drying step when the method for producing the cured product includes the drying step described later) is not particularly limited, but is preferably 1 μm or more, more preferably 1 to 100 μm, and 2 to 40 μm for further better. As long as the film thickness is within the above-mentioned range, the effect of suppressing heating unevenness at positions in the film in the electromagnetic wave irradiation step described later is remarkable, and heating can be performed quickly.

<Drying step> The said photosensitive film can be used for the process (drying process) of drying the photosensitive film (layer) formed after a film formation process (layer formation process), in order to remove a solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the photosensitive film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the photosensitive film in the drying step is preferably 50 to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The said photosensitive film is used for the exposure step of selectively exposing the photosensitive film. That is, the manufacturing method of the hardened|cured material of this invention includes the exposure process which selectively exposes the photosensitive film formed by the film formation process. Selectively exposing means exposing a part of the photosensitive film. Moreover, by selectively exposing, the exposed area (exposed part) and the unexposed area (non-exposed part) are formed on the photosensitive film. The exposure amount is not particularly limited as long as the photosensitive film can be exposed, but for example, it is preferably 50 to 10,000 mJ/cm ² and more preferably 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

Regarding the exposure wavelength, if the relationship with the light source is explained, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) ) High pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and the third harmonic is 355nm, etc. With regard to the photosensitive composition, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the photosensitive film formed from the photosensitive composition, and exposure using a mask and exposure by direct laser imaging can be mentioned. Wait.

<Heating step after exposure> The said photosensitive film can be used for the process (heating process after exposure) of heating after exposure. That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the photosensitive film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

<Development step> The said photosensitive film after exposure is used for the image development process which develops using a developing solution and forms a pattern. That is, the manufacturing method of the hardened|cured material of this invention includes the developing process which develops the photosensitive film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of the exposed part and the non-exposed part of the photosensitive film is removed, and a pattern is formed. Among them, the development of removing the non-exposed portion of the photosensitive film by the development step is called negative development, and the development of removing the exposed portion of the photosensitive film by the development step is called positive development.

[Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.

When the developing solution is an alkaline aqueous solution, examples of the alkaline compounds that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH ( Tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium oxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis(hydroxide) 2-hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass in the total mass of the developer. good.

When the developing solution contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc., for example. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc.) (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxy Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionic acid) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane Ethyl acid, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone can be preferably used ketone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Preferable examples of the sulfites include dimethylsulfoxide, and as the alcohols, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylenediol. Alcohol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are preferably used. Wait.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, development of at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly included The solution is preferred, and the developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and the developing solution including cyclopentanone is the most preferred.

When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more relative to the total mass of the developer solution. The above are excellent. Moreover, the said content may be 100 mass %.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply developer] The supply method of the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate on which the photosensitive film is formed in the developer, and a method of immersing a photosensitive film formed on the substrate using a nozzle. The film is supplied with a developer for spin-on immersion development or a method of continuously supplying the developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate. The step of liquid solution can also be repeated several times. In addition, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.

[Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).

As the organic solvent when the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably mentioned. Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

The rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate in the rinse liquid, spin immersion development on the substrate, and spraying the rinse liquid The method of supplying to the substrate and the method of continuously supplying the developer to the substrate by a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the photosensitive film after exposure through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be performed preferably at 10 to 45°C, and more preferably at 18 to 30°C.

<Electromagnetic wave irradiation procedure> The manufacturing method of the hardened|cured material of this invention includes the electromagnetic wave irradiation process which irradiates the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less to the pattern obtained by the said developing process. For example, when a photosensitive film contains specific resin mentioned later, the pattern is heated by an electromagnetic wave irradiation process, and hardening of specific resin is performed.

In the electromagnetic wave irradiation step, the electromagnetic wave may be irradiated to at least a part of the pattern obtained in the developing step, but it is preferable to irradiate the entire pattern. The irradiation amount is not particularly limited, and the temperature of the photosensitive film and the irradiation time of the electromagnetic wave may be the irradiation amount within the range described later.

The electromagnetic wave in the electromagnetic wave irradiation step is an electromagnetic wave with a wavelength of 780 nm or more and 5 μm or less, preferably an electromagnetic wave with a wavelength of 900 nm or more and 4 μm or less, and more preferably an electromagnetic wave with a wavelength of 1000 nm or more and 3.5 μm or less. In the case where the above-mentioned electromagnetic waves include electromagnetic waves of a plurality of wavelengths, the wavelength of at least one electromagnetic wave may be within the above-mentioned range. When the photosensitive composition contains a photopolymerization initiator, an aspect in which the electromagnetic wave does not include an electromagnetic wave having a wavelength of 550 nm or less is also one of the preferred aspects of the present invention. In addition, when the photosensitive composition contains a photobase generator, the generation of the base derived from the photobase generator is accelerated, so the aspect in which the above-mentioned electromagnetic wave includes an electromagnetic wave having a wavelength of 550 nm or less is also a preferred aspect of the present invention. one. In addition, it may be preferable that the above-mentioned electromagnetic waves include electromagnetic waves of various wavelengths (so-called broad electromagnetic waves) because the tolerance to the composition of the photosensitive film is high.

Examples of the exposure light source include known infrared lamps, infrared diodes, and infrared irradiation devices, and can be used without particular limitations in consideration of the wavelength of the electromagnetic wave to be irradiated, the energy of the electromagnetic wave to be irradiated, and the like. Among these, it is preferable to use a halogen heater (halogen lamp).

The temperature (maximum temperature) of the pattern in the electromagnetic wave irradiation step is not particularly limited and may be determined in consideration of the components contained in the photosensitive film, but is preferably 400°C or lower, more preferably 300°C or lower. It is more preferable that it is 250 degrees C or less, and 240 degrees C or less can also be set. The lower limit of the maximum temperature is preferably 150°C or higher, more preferably 180°C or higher.

In the electromagnetic wave irradiation step, the total time for irradiating the pattern with the electromagnetic wave is not particularly limited, and may be determined in consideration of the thickness of the photosensitive film, the components contained in the photosensitive film, and the like, but 60 minutes or less is preferable. 30 minutes or less is better.

The electromagnetic wave irradiation step is preferably carried out in an inert gas environment. Examples of the inert gas include halogen gases such as N ₂ gas and Ar gas. In addition, it is also preferable to perform the electromagnetic wave irradiation step in a reduced pressure state or in a vacuum state. Furthermore, it is also preferable to perform the electromagnetic wave irradiation step in a reducing gas environment such as H ₂ gas and formic acid gas. In these aspects, the electromagnetic wave irradiation step is preferably performed in an environment with an oxygen concentration of 1,000 ppm or less, more preferably in an environment of 100 ppm or less, and even more preferably in an environment of 10 ppm. The lower limit of the above-mentioned oxygen concentration is not particularly limited, as long as it is 0 ppm or more.

The heating rate of the pattern in the electromagnetic wave irradiation step is preferably 5°C/min or more, preferably 10°C/min or more, and 100°C/min or more from the temperature at the start of the electromagnetic wave irradiation step to the above-mentioned maximum temperature. better.

The temperature of the pattern at the start of the electromagnetic wave irradiation step is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of the electromagnetic wave irradiation step refers to the temperature when the electromagnetic wave irradiation is started in the electromagnetic wave irradiation step. For example, when the photosensitive composition contains a solvent, it is preferable to raise the temperature from a temperature lower than the boiling point of the solvent by 30 to 200°C.

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

Moreover, in the electromagnetic wave irradiation process, you may heat by another heating means. The above-mentioned heating may be performed simultaneously with the irradiation of electromagnetic waves, or may be performed before or after the irradiation of electromagnetic waves is started. As said heating means, a hotplate, an electrothermal oven, a hot air oven, etc. are mentioned, for example.

As the electromagnetic wave irradiation means in the electromagnetic wave irradiation step, for example, a known infrared irradiation device such as an infrared oven can be used without particular limitation.

The pattern may be cooled after the electromagnetic wave irradiation step is finished.

<Exposure step after development> In addition to the electromagnetic wave irradiation step described above, the pattern obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used in the post-development exposure step of exposing the pattern after the development step middle. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The manufacturing method of the cured product of the present invention may include a heating step and an exposure step after development, or may include only one of a heating step and an exposure step after development. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator can be accelerated, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step> The pattern obtained by the electromagnetic wave irradiation step can be used in a metal layer forming step of forming a metal layer on the pattern. That is, it is preferable that the manufacturing method of the hardened|cured material of this invention includes the metal layer formation process which forms a metal layer on the pattern obtained by the electromagnetic wave irradiation process.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, alloys containing these metals, copper and aluminum. More preferred, copper is further preferred.

The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution can be mentioned.

The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, in the thickest part.

<hardened product> The hardened|cured material can be obtained by the manufacturing method of the hardened|cured material of this invention. The form of the cured product is not particularly limited, and a film form, a rod form, a spherical form, a granular form, etc. can be selected according to the application. In the present invention, the obtained cured product is preferably in the form of a film. Furthermore, by patterning the photosensitive composition, the curing can also be selected for the purpose of forming a protective film on the wall surface, forming a beer hall for conduction, adjusting resistance, capacitance or internal stress, and imparting a heat release function. shape of things. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less. When the cured product is produced by the method for producing a cured product of the present invention, the shrinkage ratio is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change of the pattern after the electromagnetic wave irradiation step with respect to the pattern after the development step, and can be calculated by the following formula. Shrinkage rate [%]=100-(volume of pattern after electromagnetic wave irradiation step÷volume of pattern after developing step)×100

<Characteristics of hardened product> In the case where the photosensitive composition used in the method for producing a cured product of the present invention contains a precursor of a cyclized resin to be described later, from the viewpoint of the elongation at break of the cured product, the method for producing a cured product of the present invention can The cyclization rate in the obtained hardened material is preferably 70% or more, more preferably 80% or more, and further more preferably 90% or more. The elongation at break of the cured product obtained by the method for producing the cured product of the present invention is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. It is preferable that the glass transition temperature (Tg) of the hardened|cured material obtained by the manufacturing method of the hardened|cured material of this invention exceeds 180 degreeC, More preferably, it exceeds 200 degreeC, More preferably, it exceeds 230 degreeC.

＜Use＞ Examples of fields to which the method for producing a cured product of the present invention or a cured product obtained by the method for producing a cured product of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for rewiring layers, stress buffer films, and the like. . In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

In addition, the manufacturing method of the cured product of the present invention or the cured product obtained by the manufacturing method of the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates and screen plates, the use of etching molding components, electronics, especially microelectronics. In the manufacture of protective paint and dielectric layers, etc.

(Laminated body and method for producing the laminated body) The layered product of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers formed of a cured product, and may be a layered body formed by stacking three or more layers. At least one of the two or more layers formed of the cured product included in the above-mentioned layered product is a layer formed of the cured product of the present invention, and suppresses the shrinkage of the cured product or the deformation of the cured product accompanying the shrinkage. From a viewpoint, it is also preferable that all the layers formed of the cured product included in the above-mentioned laminate are layers formed of the cured product of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include the process of repeating the manufacturing method of the laminated body of this invention several times.

The layered product of the present invention includes two or more layers formed of a cured product, and an aspect in which a metal layer is included between any of the layers formed of the cured product is preferred. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation step of forming a metal layer on the layer formed of the hardened|cured material during the manufacturing method of the hardened|cured material performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layer structure in which at least three layers of a first layer made of a cured product, a metal layer, and a second layer of a cured product are laminated in this order can be mentioned as a preferred one. . It is preferable that the above-mentioned first layer formed from the hardened product and the above-mentioned second layer formed from the hardened product are both layers formed from the hardened product of the present invention. The photosensitive composition used to form the above-mentioned first layer formed of the hardened material and the photosensitive composition used to form the above-mentioned second layer formed of the hardened material may have the same composition or may have different compositions. composition. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

<Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process. The lamination step includes performing (a) film forming step (layer forming step), (b) exposure step, (c) developing step, (d) electromagnetic wave irradiation step again in sequence on the surface of the pattern (resin layer) or metal layer. a series of steps. However, at least one of the (a) film formation step and the (d) electromagnetic wave irradiation step may be repeated. Also, after (d) the electromagnetic wave irradiation step, (e) a metal layer forming step may be further included. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.

When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned electromagnetic wave irradiation step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferable to form a layer formed of a cured product so as to cover the above-mentioned metal layer after the metal layer is provided. Specifically, (a) film forming step, (b) exposure step, (c) developing step, (d) electromagnetic wave irradiation step (e) metal layer forming step are sequentially repeated, or (a) A state of the film forming step, (d) the electromagnetic wave irradiation step, and (e) the metal layer forming step. By alternately performing the lamination step of laminating the layer formed of the cured product and the metal layer forming step, the layer formed of the cured product of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment step) It is preferable that the manufacturing method of the layered body of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the layer formed of the cured product to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step for the layer formed of the cured product after the above-mentioned development step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the layer formed of the hardened material, or may be performed on at least a part of both the metal layer and the layer formed of the hardened material. conduct. It is preferable to perform surface activation treatment on at least a part of the metal layer, and it is preferable to perform surface activation treatment on a part or the whole of the region of the metal layer where the layer formed of the hardened material is formed on the surface. In this way, by subjecting the surface of the metal layer to the surface activation treatment, the adhesion to the layer formed of the cured product provided on the surface can be improved. Moreover, it is preferable to also perform a surface activation process with respect to a part or all of the layer which consists of hardened|cured material. In this way, by subjecting the surface of the layer formed of the cured product to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activation treatment can be improved. In particular, when a layer formed of a cured product is hardened, such as in the case of performing negative development, it is less likely to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment, corona discharge treatment, corona discharge treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) Etching treatment of CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in Immersion treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma using oxygen as a raw material gas Handling is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , and most preferably 10,000-50,000 J/m ² .

(Manufacturing method of semiconductor element) The present invention also discloses a method for producing a semiconductor element including the method for producing the cured product of the present invention or the method for producing the laminate of the present invention. As a specific example of a semiconductor element in which the method for producing the cured product of the present invention is used in the formation of the interlayer insulating film for rewiring layers, reference can be made to the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the paragraphs of FIG. 1 . record, and incorporate these contents into this manual.

(photosensitive composition) The photosensitive composition is a composition for forming a photosensitive film in the film forming step in the method for producing the cured product of the present invention. It is preferable that the photosensitive composition contains a curable resin, and it is more preferable that it contains a thermosetting resin. In addition, the photosensitive composition includes at least one resin ( Hereinafter, it is also referred to as "specific resin".) Preferably, at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor is included. Resin is better. It is preferable that the photosensitive composition contains the polymerizable compound mentioned later. Moreover, it is preferable that the photosensitive composition contains a photopolymerization initiator or a photoacid generator described later. Hereinafter, the details of each component contained in the photosensitive composition will be described.

＜Specific resin＞ The photosensitive composition comprises at least one resin (“Specific resin") is preferred. The photosensitive composition preferably includes at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyimide imide precursors as the specific resin, including polyimide precursors. The imine precursor is more preferable as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. In particular, when the specific resin has a radically polymerizable group, it is preferable that the photosensitive composition contains a radical polymerization initiator described later, and it is more preferable that the photosensitive composition includes a radical polymerization initiator described later and a radical crosslinking agent described later. . Furthermore, the sensitizer mentioned later can be contained as needed. From such a photosensitive composition, for example, a negative photosensitive film is formed. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the photosensitive composition contains the photoacid generator mentioned later. From such a photosensitive composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 1]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent hydrogen Atom or a monovalent organic group.

A ¹ and A ² in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R ¹¹¹ in formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond and may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, the group includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.

式中，A表示單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [Chemical formula 2]

In the formula, A represents a single bond or a divalent linking group, and is selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C(=O)-, and -S- which may be substituted by a fluorine atom. , -SO ₂ -, -NHCO- or groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C ( CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine cyclohexane 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'-di Methylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenylene and 3,3-diaminodiphenylene, 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-amine) phenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane 3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine bis[4-(4-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(2 -Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene -Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine diphenylmethane, 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'-diamine Amino biphenyl, 9,9'-bis(4-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octa Methylpentasiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, bis Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminobenzene) base) 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(trifluoropropane) Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) diphenyl bismuth, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl bismuth, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least 1 of ,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl a diamine.

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

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

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

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 【化學式4】

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為提供式（51）或式（61）的結構之二胺，可以舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 3]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the formula (2). Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 4]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in the formula (2). As the diamine which provides the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

式（5）中，R ¹¹²為單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基團為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中的2價的基團為進一步較佳。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 5]

In formula (5), R ¹¹² is a single bond or a divalent linking group, selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, which may be substituted by a fluorine atom , -SO ₂ - and -NHCO- and the groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO ₂ - are more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, The divalent group in the group of -S- and -SO ₂ - is more preferable.

式（O）中，R ¹¹⁵表示4價的有機基。R ¹¹⁵的較佳範圍與式（2）中之R ¹¹⁵的含義相同，較佳範圍亦相同。 Specific examples of R ¹¹⁵ include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 6]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' - Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-Dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -Tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned as a preferable example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may also have an OH group. More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxy group. Moreover, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, or the like, a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxane group. azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[Chemical formula 7]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group or a polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and the like. base, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH) CH ₂ -, polyalkyleneoxy, ethylidene, propylidene and other alkylene groups, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkeneoxy groups are more preferred, and alkylene groups such as ethylidene and propylidene groups or polyalkeneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, it is preferable that the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group obtained by bonding two propeneoxy groups is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately, etc. patterned. Several preferred aspects such as vinyloxy in these groups are repeated as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, a polyimide precursor may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as the diamine, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基，R ¹¹³及R ¹¹⁴中的至少一者為包含聚合性基之基團，兩者為包含聚合性基之基團為較佳。 Preferably, the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain the repeating unit represented by the formula (2-A), the width of the exposure latitude can be increased. Formula (2-A) [Chemical Formula 8]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably a group containing a polymerizable group.

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

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be repeating units represented by formula (2).

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 further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. In addition, when the photosensitive composition contains a plurality of polyimide precursors as the 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 above-mentioned ranges. . Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.

式（3）中，R ¹²¹表示2價的有機基，R ¹²²表示4價的有機基，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] Although the structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 9]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), respectively, and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, including a linear or branched (preferably linear) aliphatic group and 2 -COOH dicarboxylic acids are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and further preferably 4 to 15, 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexanoic acid Fluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoroic acid Suberic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid , hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tridecanedioic acid acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacosanedioic acid, Tridecanedioic acid, tridecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [Chemical formula 10]

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

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

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-的群組中之2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 11]

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

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

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as that of R ¹¹⁵ in the above formula (2), and the preferred range is also the same. R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-diaminophenol. Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- 3-Hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 ,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

式中，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²為上述式所表示之結構亦較佳。在R ¹²²為上述式所表示之結構之情況下，在共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且其他2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 12]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Moreover, it is also preferable that R ¹²² is a structure represented by the above formula. In the case where R ¹²² is a structure represented by the above formula, among the total of 4 * and #, any two are the bonding site to the nitrogen atom to which R ¹²² in the formula (3) is bonded, and the other two are Preferably, it is the bonding site of the oxygen atom bonded to R ¹²² in the formula (3), and two * are the bonding sites of the oxygen atom bonded to R ¹²² in the formula (3), and 2 # is the bonding site with the nitrogen atom bonded to R ¹²² in the formula (3), or two * are the bonding sites with the nitrogen atom bonded with R ¹²² in the formula (3) and two # More preferably, it is the bonding site of the oxygen atom bonded to R ¹²² in the formula (3), and 2 * are the bonding sites of the oxygen atom bonded to R ¹²² in the formula (3), and 2 It is more preferable that # is the bonding site to the nitrogen atom bonded to R ¹²² in the formula (3).

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 13]

In formula (As), R ₁ is selected from hydrogen atom, alkylene group, substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or the following formula An organic group in the group of (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [Chemical formula 14]

(In the formula (A-sc), * represents a bond with the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, also on R ₃ will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it will be higher when hardening at a low temperature is further improved. It is particularly preferable in terms of the effect of the cyclization rate.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the effect of maintaining high transparency to i-rays and high cyclization rate during curing at low temperature is preferable.

In addition, in the above formula (As), it is more preferable that R ₁ is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for R ₁ include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, wherein high transparency to i-rays and low temperature are maintained while maintaining high transparency. -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ - is better.

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

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Laid-Open No. 2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these, it goes without saying.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may contain other kinds of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in terms of suppressing the occurrence of warpage accompanying ring closure.

式（SL）中，Z具有a結構和b結構，R ^1s為氫原子或碳數1～10的烴基，R ^2s為碳數1～10的烴基，R ^3s、R ^4s、R ^5s、R ^6s中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。 [Chemical formula 15]

In formula (SL), Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R ^2s is a hydrocarbon group with 1 to 10 carbon atoms, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and a+b is 100 mol %.

In the formula (SL), as preferable Z, those in which R ^5s and R ^6s in the structure b are phenyl groups can be mentioned. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is further preferred, and 2.2 or less is preferred. for further better. Moreover, in the case where the photosensitive composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polybenzoxazole precursor are within the above ranges: better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.

式（PAI-2）中，R ¹¹⁷表示3價的有機基，R ¹¹¹表示2價的有機基，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價的有機基。 [Polyamide imide precursor] It is preferable that the polyamide imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 16]

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In the formula (PAI-2), R ¹¹⁷ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear 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, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two carboxyl groups among the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamide imide precursor, a branched aliphatic, cyclic, or aromatic tricarboxylic acid compound, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.

Specifically, the tricarboxylic acid compound includes a linear 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, A tricarboxylic acid compound of an aromatic group having 6 to 20 carbon atoms, a single bond, or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond is preferable. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group is more preferable.

In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride ammonium chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in the above formula (2), respectively, and the preferred embodiments are also the same.

The polyamidoimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [Chemical formula 17]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear 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, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, a single bond, or a dicarboxylic acid compound or a dicarboxylic acid dihalide of a group obtained by combining two or more of these groups by a linking group is relatively Preferably, a dicarboxylic acid compound or dicarboxylic acid dihalogenation containing an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group Things are better.

Further, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in the above formula (2), and the preferred aspects are also the same.

Moreover, it is also preferable that the polyamide imide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure may be copolymerized with a polyamide imide precursor. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

As one embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) can be mentioned. The total content of the indicated repeating units is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamide imide precursor except the terminal may be repeating units represented by formula (PAI-2), and formula (PAI-1). Any one of the repeating unit and the repeating unit represented by formula (2). Moreover, as another embodiment of the polyamide imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned In the form of more than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal may be the repeating units represented by the formula (PAI-2) or the formula (PAI-1). Any of the repeating units.

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, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable. The molecular weight 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. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the photosensitive composition includes a plurality of polyamide imide precursors as the specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges Inside is better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imide precursors as one resin are respectively within the above ranges.

[Production method of polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide A method of esterifying an amine acid with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by A method in which tetracarboxylic dianhydride and alcohol are used to obtain a diester, and the remaining dicarboxylic acid is halogenated using a halogenating agent, followed by a method of reacting it with a diamine. In the above-mentioned production method, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated using a halogenating agent and reacted with a diamine is more preferable. As the above-mentioned condensing agent, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is performed. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. , dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine and the like.

-Capping agent- In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amine group remaining at the resin end of the polyimide precursor or the like. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin end, examples of the blocking agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, from the viewpoint of reactivity and film stability. , it is better to use monohydric alcohols, phenols or monoamines. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloroethanol Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6- aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7- aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminowater Sylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred sealants for amine groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., carboxylic acid anhydrides, carboxylic acid chlorides are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic acid anhydride, etc. In addition, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, trimethyl acetyl chloride, cyclohexane methyl chloride, 2-ethyl chloride can be mentioned. Hexyl chloride, cinnamon chloride, 1-adamantanecarboxy chloride, heptafluorobutane chloride, stearate chloride, benzyl chloride, etc.

-Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof to make the polymer into a It is possible to obtain a polyimide precursor or the like by precipitation as a solid by analysis and drying. In order to improve the degree of purification, operations such as redissolving, reprecipitating, and drying the polyimide precursor and the like may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

[Epoxy resin] The epoxy resin is not particularly limited, and examples thereof include novolak-type epoxy resins, bisphenol-type epoxy resins, glycidylamine-type epoxy resins, glycidyl-ether-type epoxy resins, and trisphenolmethane-type epoxy resins. Resin, triphenol propane type epoxy resin, alkyl modified triphenol methane type epoxy resin, epoxy resin containing three nuclei, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin , Naphthalene type epoxy resin, novolac aralkyl type epoxy resin having at least any one of a phenylene skeleton and a biphenylene skeleton, and at least any one of a phenylene skeleton and a biphenylene skeleton Aralkyl-type epoxy resins such as naphthol aralkyl-type epoxy resins, aliphatic epoxy resins, and the like. Moreover, when a specific resin contains an epoxy resin, the epoxy compound described in the polymerizable compound mentioned later can be used as a specific resin.

[Phenolic resin] As a phenol resin, a novolac resin, a vinyl polymer, etc. are mentioned, for example. As said novolak resin, the thing obtained by condensing phenols and aldehydes in the presence of an acid catalyst is mentioned, for example. Examples of the above-mentioned phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, gallic phenol, naphthol, and bisphenol A. . As said aldehyde, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, etc. are mentioned, for example. The above-mentioned phenols and aldehydes can be used alone or in combination of two or more. As a specific example of the said novolak resin, the condensation product of m-cresol, p-cresol, or these mixtures, and formalin is mentioned, for example. The molecular weight distribution of the above-mentioned novolak resin can be adjusted by methods such as classification. Moreover, the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, can be mixed with the said novolak resin.

〔content〕 The content of the specific resin in the photosensitive composition is preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, and 50 mass % or more with respect to the total solid content of the photosensitive composition for further better. In addition, the content of the resin in the photosensitive composition is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % with respect to the total solid content of the photosensitive composition. The following is still more preferable, and 95 mass % or less is still more preferable. The photosensitive composition may contain only 1 type of specific resin, or may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

Moreover, it is also preferable that the photosensitive composition contains at least two kinds of resins. Specifically, the photosensitive composition may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the photosensitive composition contains two or more kinds of specific resins, for example, two or more kinds which are polyimide precursors and are derived from dianhydride-derived structures (R ¹¹⁵ described in the above formula (2)) are contained in two or more kinds The polyimide precursor is preferred.

<Other resins> The photosensitive composition may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include polyamides, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, urethane resins, butyral resins, Styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a photosensitive composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 ^-3 ) molar/g or more) (meth)acrylic resin is added to the photosensitive composition, whereby the coatability of the photosensitive composition, the solvent resistance of the pattern (hardened product), and the like can be improved.

When the photosensitive composition contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 1% by mass or more with respect to the total solid content of the photosensitive composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. The content of other resins in the photosensitive composition is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and 60% by mass or less with respect to the total solid content of the photosensitive composition. % or less is still more preferable, and 50 mass % or less is still more preferable. Moreover, as a preferable aspect of a photosensitive composition, the aspect which content of other resin is low content can also be used. In the above aspect, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and 5% by mass or less with respect to the total solid content of the photosensitive composition. For still more preferable, 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The photosensitive composition may contain only 1 type of other resin, or may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

<Polymerizable compound> It is preferable that the photosensitive composition contains a polymerizable compound. Moreover, it is preferable that the photosensitive composition contains a bifunctional or more polymerizable compound, and it is also one of preferable aspects that a trifunctional or more polymerizable compound is contained. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical crosslinking agent] It is preferable that the photosensitive composition contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloyl. Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the photosensitive composition contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. .

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

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used, Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.

Moreover, it is also preferable that the radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane etc. Compounds obtained by adding ethylene oxide or propylene oxide to alcohol followed by (meth)acrylic esterification, such as Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication Sho 51 - Urethane (meth)acrylates described in each publication of No. 037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 Polyester acrylates, polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, or methacrylates, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

Moreover, as preferable radical crosslinking agent substances other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. A compound having a perylene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo resin.

Furthermore, as other examples, the specific unsaturated compounds described in JP 46-043946 A, JP 01-040337 A, JP 01-040336 A, or JP 02 - Vinylphosphonic acid-based compounds and the like described in Gazette 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the etc. are incorporated into this manual.

In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds, which are described as formula (1) and formula (2) together with specific examples thereof, can also be used as a radical crosslinking agent in a polyfunctional alcohol. A compound obtained by adding ethylene oxide or propylene oxide and then (meth)acrylated.

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

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

Commercially available products of the radical crosslinking agent include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 TPA-330 of trifunctional acrylate of isobutyloxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T , UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As the radical crosslinking agent, for example, carbamic acid described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Ethyl acrylates, those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have ethylene oxide. Urethane compounds of the skeleton are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

From the viewpoints of pattern analysis properties and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate as the photosensitive composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bond, with urethane bond The 2-functional methacrylate. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the photosensitive composition, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (cured product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. (meth) Acrylic derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. In addition, as a bifunctional or more than bifunctional radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of a photosensitive composition. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount is in the said range.

[Other cross-linking agents] It is also preferable that the photosensitive composition contains another crosslinking agent different from the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and has a plurality of crosslinking agents in the molecule, which are promoted by the above-mentioned photoacid generator or photobase generator to facilitate interaction with the composition. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the photosensitive composition contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and the photosensitive composition preferably contains at least one compound selected from the group consisting of the glycoluril-based crosslinking agent described below and At least one compound in the group of the melamine-based crosslinking agent is more preferable.

As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group directly in the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trisium are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[Chemical formula 18]

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include various compounds of the following general formula.

[Chemical formula 19]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R ⁵ represents a group that can be removed by the action of an acid.)). R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ include a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is released by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 . Out-C(R ₃₆ )(R ₃₇ )(R ₃₈ ),-C(R ₃₆ )(R ₃₇ )(OR ₃₉ ),-C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may have a well-known substituent within the range which can obtain the effect of this invention.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As these groups, a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group, and the like are preferable. Further preferred are tertiary alkyl ester groups and acetal ester groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an acyloxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an acyloxymethyl group is mentioned. As a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, the following various compounds are mentioned, However, It is not limited to these.

[Chemical formula 20]

[Chemical formula 21]

As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril Methylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril and other glycoluril-based cross-linking agents; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents, Monomethylolated Propylene Urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine , monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, mono Butoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.

In addition, as a compound having at least one group selected from the group consisting of methylol and alkoxymethyl, a direct bond on an aromatic ring (preferably a benzene ring) can also be preferably used A compound having at least one group selected from the group consisting of methylol and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

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

Moreover, it is also preferable that the photosensitive composition contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

-Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warpage of the photosensitive composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy epoxy silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) 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) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (product names above, 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 product names above, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[Chemical formula 22]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

Among the above-mentioned structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

-Oxetane compounds (compounds with an oxetane group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxy oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121 and OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-Benzoxazole compounds (compounds having a benzoxazolyl group)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzoxazine compound is preferred without degassing during hardening, thereby further reducing thermal shrinkage and suppressing the occurrence of warpage.

Preferable examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine, (the above are the product names, manufactured by Shikoku Chemicals Corporation), and benzoxazine of polyhydroxystyrene resin. Adduct, novolac-type dihydrobenzoxazine compound. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents 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 1.0 to 10% by mass relative to the total solid content of the photosensitive composition. Excellent. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

<Organometallic complex> From the viewpoint of chemical resistance, it is preferable that the photosensitive composition contains an organometallic complex. Organometallic complexes only need to be organic complexes containing metal atoms, but complexes containing metal atoms and organic groups are preferred, and compounds in which organic groups coordinate metal atoms are more preferred, and metallocene compounds are preferred. for further better. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. Although it does not specifically limit as said organic group, The group which consists of a hydrocarbon group or a combination of a hydrocarbon group and a hetero atom is preferable. As the hetero atom, an oxygen atom, a sulfur atom and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but a metal corresponding to a Group 4 element is preferred, and at least one metal selected from the group consisting of titanium, zirconium and hafnium is more preferred , at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one type of metal atom may be contained, or two or more types of metal atoms may be contained.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound, a zirconocene compound or a hafnocene compound is More preferably, titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.

The aspect that the organometallic complex has the initiation energy of photo-radical polymerization is also one of the preferred aspects of the present invention. In the present invention, having photoradical polymerization initiation energy means that a radical capable of initiating radical polymerization can be generated by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, it can be The presence or absence of photoradical polymerization initiation energy was confirmed by confirming the disappearance of the radical crosslinking agent. When confirming the disappearance or not, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it may be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). In the case that the organometallic complex has the initiation energy of photo-radical polymerization, it is preferred that the organometallic complex is a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and two Titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. In the case where the organometallic complex does not have the initiation energy of photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, titanium chelates, At least one compound selected from the group consisting of a zirconocene compound and a hafnocene compound is preferred, and at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound and a hafnocene compound is more preferred. Preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.

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

式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [Chemical formula 23]

In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, and a titanium atom or a zirconium atom is further preferable , titanium atoms are particularly good. Examples of the aromatic group in R of the formula (P) include aromatic groups having 6 to 20 carbon atoms, and preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl, etc. As the alkyl group in R of the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl group, ethyl group, propyl group, and octyl group are mentioned. , isopropyl, tert-butyl, isoamyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. As the halogen atom in the above-mentioned R, F, Cl, Br and I can be mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, and propyl groups are mentioned. base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. The above R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryl Oxycarbonyl, acyloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

Specific examples of the organometallic complex are not particularly limited, but tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate) can be exemplified. Titanium, diisopropoxybis(acetoacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl) base)phenyl)titanium, pentamethylcyclopentadienyltrimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following said compound. [Chemical formula 24]

In addition to this, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the photosensitive composition. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

[Polymerization initiator] It is preferable that the photosensitive composition contains a polymerization initiator capable of starting polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Moreover, it is preferable that the photosensitive composition of this invention contains the metallocene compound mentioned later as a polymerization initiator from the viewpoint of the chemical resistance of a hardened|cured material and elongation at break. Preferably, the photopolymerization initiator is a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer of photoexcitation.

Preferably, the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L/mol ^-1 /cm ^-1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in JP 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in JP 2019-044030 A, the peracid-based initiator described in JP 2019-167313 A, These contents are also incorporated into this manual.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and this content is incorporated in the present specification. Among the commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the This content is incorporated into this manual.

As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: all made by BASF).

As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are BASF Corporation) can be used system).

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength is matched to a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in the present specification.

As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Corporation), and the like.

As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, so it is particularly preferable.

Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and compounds described in JP 2006-342166 A. Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP 2004-534797 A, JP 2006-342166 A Compounds described, compounds described in JP 2017-019766 A, compounds described in JP 6065596 A, compounds described in International Publication No. 2015/152153, International Publication No. 2017/051680 The compounds described in JP 2017-198865 A, 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., and the contents are incorporated into this manual.

Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the photosensitive composition, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 25]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photo-radical polymerization initiator 2) described in Gazette No. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used . In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 26]

As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in Japanese Patent Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in the present specification.

As the photoradical polymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 is mentioned, and the content is incorporated in this specification.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471, and the contents thereof are incorporated into the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A. The compound is the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated into the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound obtained by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 into which an electron withdrawing group is introduced can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, and an acyl group is more preferable, and a benzyl group is still more preferable because of the ease of forming a film excellent in light resistance. The benzyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkenyl group, alkylthio group, arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio group or an amine group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、亞膦醯基、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基； 其中，R ^X10～R ^X14中的至少1個為拉電子基團。 The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [Chemical formula 27]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphonide group, carbamoyl group or sulfamoyl group, R ^X2 represents alkyl, alkene alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl group, arylsulfonyl group, aryloxy group or amine group, R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent; wherein, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X12 is an electron withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated in the present specification.

As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group shown in JP-A No. 2009-191061 can be mentioned. , and incorporate it into this manual.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is more preferable to use at least one compound in the group of ketone compounds, and it is especially preferable to use a metallocene compound.

In addition, as the photoradical polymerization initiator, N, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by condensed with aromatic rings, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 28]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group or C1-20 alkyl, C1-12 alkoxy, halogen atom, cyclopentyl, cyclohexyl, C2-12 alkenyl, interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of the alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms, R ^I01 is a group represented by formula (II) or the same as R ^I00 R ^I02 to R ^I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons or a halogen atom.

[Chemical formula 29]

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

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in the present specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation over time becomes difficult, so that the stability over time of the photosensitive composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The oxime ester photoinitiator and the like described, and the contents are incorporated into this specification.

When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass % with respect to the total solid content of the photosensitive composition, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass % %, more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

[Sensitizer] The photosensitive composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with the thermal radical polymerization initiator, the photoradical polymerization initiator, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator are decomposed by chemical change, and a radical, an acid, or a base is generated. As sensitizers that can be used, ethanolamine-based, benzophenone-based, Michler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, and anthraquinone-based sensitizers can be used series, anthracene series, anthrapyridone series, benzylidene series, oxocyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azo series Compounds such as methine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series, etc. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)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-dimethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3 -Methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylamine isoamyl benzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylamine) styryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole , 2-(p-dimethylaminobenzyl)styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide Wait. In addition, other sensitizing dyes can be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

When the photosensitive composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the photosensitive composition. The mass % is more preferable. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent] The photosensitive composition may contain a chain transfer agent. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, a compound having a compound for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) polymerized thiocarbonylthio dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. These can generate free radicals by supplying hydrogen to the less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.

In addition, as a chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO 2015/199219 can also be used, and the contents are incorporated in the present specification.

When the photosensitive composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive composition, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

[Photoacid generator] It is preferable that the photosensitive composition contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating an acid by exposure to light is preferred. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives. , Antimony derivatives, halogen peroxides, sulfonamides, etc.

Examples of the photoacid generator used in the photosensitive composition include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of mechanical properties of the formed film, oxime esters are preferred.

Examples of the quinonediazide compound include a sulfonic acid ester bond of quinonediazide to a monovalent or polyvalent hydroxy compound, and a sulfonic acid sulfonamide bond of quinonediazide to a monovalent or polyvalent amine compound. On the other hand, those obtained are those obtained by the sulfonate bond of quinonediazide and/or the sulfonamide bond to the polyhydroxypolyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but on average, more than 40 mol% of the total functional groups are substituted with quinonediazide as better. By containing such a quinonediazide compound, it is possible to obtain a photosensitive composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, and 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, Methylenetri-FR-CR, BisRS-26X, 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 (the product name above, manufactured by Honshu Chemical Industry Co., Ltd.), 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 the product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethylacetate Oxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxydiol Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.

Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc., but not limited on such.

In addition, specific examples of the polyhydroxypolyamine compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but It is not limited to these.

Among these, it is preferable to contain a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. Thereby, higher sensitivity and higher resolution to i-ray exposure can be obtained.

The content of the quinonediazide compound used in the photosensitive composition is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, with respect to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed portion and the unexposed portion can be obtained, and thus higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the following formula (OS-103), the formula (OS-104), or the formula (OS-105) The represented oxime sulfonate compounds are preferred.

【Chemical formula 30】

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X ³ exist, they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ³ may have a substituent. As the alkyl group in the aforementioned X ³ , a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of ^X3 may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In formula (OS-1), m3 is ³ , ^X3 is a methyl group, the substitution position of X3 is an ortho position, and ^R34 is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include those in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A. The following compounds are described, and these contents are incorporated into this specification.

[Chemical formula 31]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 which independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. Atom, sometimes there are plural R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl group represented by R ^s1 ( It is preferable to have 4 to 30 carbon atoms) within a range in which the effects of the present invention can be obtained, and may have a known substituent.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1-12) or an aryl group (preferably with a carbon number of 6-30), A hydrogen atom or an alkyl group is more preferable. In the compound sometimes there are more than 2 R ^s2 , one or two is preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom, more preferably, one is an alkyl group, an aryl group or a halogen atom Alkyl groups and the remainder are hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R ^s2 may have a known substituent within a range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.

In the formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is 2. good. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the above formula (OS-104) ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 32]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms , methyl is particularly good.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or a mixture may be used. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraphs 0088 to 0095 of Japanese Patent Laid-Open No. 2011-209692 and Japanese Patent Laid-Open No. 2015-194674. Compounds described in paragraphs 0168 to 0194 of the gazette, and these contents are incorporated into the present specification.

As another preferable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 33]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group , cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, and an alkylcarbonyl group , arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

作為市售品，可以舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製）、MBZ-101（Midori Kagaku Co.,Ltd.製）等。 More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any of them, respectively, or a mixture may be used. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195-0207 of JP-A No. 2015-194674 can be exemplified. These contents are incorporated into this manual. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 34]

As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 35]

Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Laid-Open Japanese Patent Laid-Open No. 48-36281, Japanese Patent Laid-Open No. 55-32070, Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 61-169837 Sho 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, and these contents are incorporated into the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: an S-triazole compound can be mentioned as a preferable example. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-s-tris-s-s-s-s-s-s-s-s-s-s-s-s-s-s-s-derivatives, for example, 2,4,6 -Tris(monochloromethyl)-s-tris-tris, 2,4,6-tris(dichloromethyl)-s-tris-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-( α,α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) methyl)-s-tris-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-[1-(p-methoxyphenyl)-2 ,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris, 2-styryl-4,6-bis(trichloromethyl)-s-s-tris, 2 -(p-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) base)-s-tris-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl) base)-s-tris-tris, 2,4,6-tris (dibromomethyl)-s-tris, 2,4,6-tris (tribromomethyl)-s-tris, 2-methyl -4,6-bis(tribromomethyl)-s-tris-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-s-tris, etc.

As the organoborate compound, for example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98" .Proceeding April 19-22, 1998, the organic borate described in "Chicago", etc., Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561 Organoboronium complexes or organoboroxonium complexes, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 9-188710 The organoboron phosphonium complexes described in Gazette No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-306527 Organoboron transition metal complex complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are taken as specific examples, and these content are incorporated in this specification.

The diazonium compound and the diazodione compound described in Japanese Patent Laid-Open No. 61-166544, Japanese Patent Laid-Open No. 2002-328465 and the like can be exemplified as the dioxane compound.

Examples of the above-mentioned onium salt compounds include the diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21,423 (1980), and U.S. Patent No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Pat. No. 4,069,055, US Pat. No. 4,069,056, European Patent No. 104,143, US Pat. No., each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, The permalate salts described in the respective specifications of US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307(1977), Selenium salts, C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. (1988), arsenic salts, onium salts such as pyridinium salts, etc., and these contents are incorporated into the present specification.

式（RI-I）中，Ar ₁₁表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₁₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar ₂₁、Ar ₂₂各自獨立地表示可以具有1～6個取代基的碳數1～20的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₂₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R ₃₁、R ₃₂、R ₃₃各自獨立地表示可以具有1～6個取代基之碳數6～20的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₃₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 Examples of the onium salt include those represented by the following general formulae (RI-I) to (RI-III). [Chemical formula 36]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferable. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkylamide group with 1 to 12 carbon atoms in the alkyl group Or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents having 6 to 20 carbon atoms, preferably , from the viewpoint of reactivity and stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. alkoxy group having 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom, monoalkylamine group having 1 to 12 carbon atoms, dialkylamine group having 1 to 12 carbon atoms each independently, Alkyl amido group or aryl amido group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, thioalkyl group having 1 to 12 carbon atoms Thioaryl. Z ₃₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

【化學式38】

【化學式39】

【化學式40】

Specific examples of preferable photoacid generators include the following. [Chemical formula 37]

[Chemical formula 38]

[Chemical formula 39]

【Chemical formula 40】

The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % with respect to the total solid content of the photosensitive composition. % is still more preferable, and it is still more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. When using a plurality of types in combination, it is preferable that these total amounts are within the above-mentioned range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.

<Alkali generator> The photosensitive composition may contain an alkali generator. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for a photosensitive composition, a thermal alkali generator and a photobase generator are mentioned. In particular, when the photosensitive composition contains a precursor of a cyclized resin, it is preferable that the photosensitive composition contains an alkali generator. By incorporating a thermal alkali generator into the photosensitive composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties and chemical resistance, for example, as a rewiring included in a semiconductor package. The performance of the interlayer insulating film for layers becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 41]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a condensed ring formed by condensing a monocyclic ring or two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The single ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or arane A base (preferably with a carbon number of 7 to 25, more preferably 7 to 19, and further preferably 7 to 12) is preferable. These groups may have a substituent within a range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12) as Preferably, optionally substituted cycloalkyl (3-24 carbon atoms are preferred, 3-18 are more preferred, 3-12 are further preferred), and optionally substituted cyclohexyl is further preferred. good.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and aryl (preferably having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms). is more preferred, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl (carbon number 7-23) is better, 7-19 is better, 7-12 is further better), aralkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), alkane Oxy group (preferably carbon number 1-24, more preferably 2-18, more preferably 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6- 12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), aralkenyl and aralkoxy are preferred. Rb ³ may have a substituent within the range in which the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 42]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, and 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ¹³ is preferably an aralkyl group.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 11), and hydrogen atom is more preferred.

Rb ³⁵ is alkyl (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are more preferable), aryl group is preferable.

Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 43]

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl group is preferred. Rb ¹⁷ is an alkyl group (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.

[Chemical formula 44]

In the formula (B3), L represents a hydrocarbon group, and the hydrocarbon group is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 above. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, the "connection chain" refers to the one that connects the connection objects in the shortest (minimum number of atoms) among the atomic chains on the path connecting the two atoms of the connection object or the group of connecting atoms. For example, in the compound represented by the following formula, L is composed of phenylene ethylidene, and has ethylidene as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is four. [Chemical formula 45]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned 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, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator include, for example, compounds described in Paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in Paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). [Chemical formula 46]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking 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.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , since the basicity of the generated base is high, it is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of chain alkyl groups and cyclic alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Groups related to the combination of a chain alkyl group and a cyclic alkyl group include, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, it is preferable that R ^N1 and R ^N2 are alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the bases generated by decomposition described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesiveness at the time of lamination with a metal (for example, copper).

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.

The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.

As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.

As the base generator, the following examples can be given, but the present invention is not limited to these.

[Chemical formula 47]

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

Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 48]

Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 49]

When the photosensitive composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the photosensitive composition. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

＜Solvent＞ It is preferable that the photosensitive composition contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane 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-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, 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.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextran ketone, and dihydrodextran Sugar ketones and the like are preferred.

As cyclic hydrocarbons, aromatic hydrocarbons, such as toluene, xylene, and anisole, and cyclic terpenes, such as limonene, are mentioned as preferable ones, for example.

As the sulfites, for example, dimethyl sulfite can be mentioned as a preferable one.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.

Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene 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 monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., it is also preferable to mix two or more types.

In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone, one kind of solvent or two or more kinds of solvents The mixed solvent is preferred. It is particularly preferred to use dimethylsulfoxide and γ-butyrolactone together or N-methyl-2-pyrrolidone and ethyl lactate together.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the photosensitive composition, It is more preferable to set it as 10-70 mass %, and it is more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The photosensitive composition may contain only one type of solvent, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the photosensitive composition contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wiring, and the like. Examples of the metal adhesion improver include alkoxysilyl-containing silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having sulfonamide structures, compounds having thiourea, and phosphoric acid derivatives. Compounds, β-ketoester compounds, amine compounds, etc.

[Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP-A No. 2018-173573 are incorporated herein by reference. Moreover, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

【Chemical formula 50】

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include aluminum tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, aluminum ethylacetate diisopropoxide, and the like.

In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the vulcanized compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.01 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the resin A. By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

<Migration inhibitor> It is preferable that the photosensitive composition further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetra azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, with sulfur Urea and hydrogen thio compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 compounds, etc., and these contents are incorporated into this specification.

Specific examples of the migration inhibitor include the following compounds.

【Chemical formula 51】

When the photosensitive composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass relative to the total solid content of the photosensitive composition. The mass % is more preferable.

Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

<Polymerization inhibitor> It is preferable that the photosensitive composition contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, and the like .

As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol are preferably used , gallic phenol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butyl) phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-benzene Hydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2 ,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-Nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, 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-tris𠯤 -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetrakis Methylpiperidine 1-oxyl radical, phenothiazine, phenothiazine, 1,1-diphenyl-2-pyrrole hydrazine, dibutyldithiocopper(II), nitrobenzene, N-idene Nitro-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, Tabon (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2 ]-non-2-ene-N,N-dicarbonyl) and so on. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, and the contents are incorporated into the present specification. .

When the photosensitive composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, preferably 0.02 to 15 mass %, more preferably 0.05 to 10 mass % with respect to the total solid content of the photosensitive composition. % is further preferred.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

＜Acid scavenger＞ It is preferable that the photosensitive composition contains an acid scavenger in order to reduce the performance change with time from exposure to heating. Among them, the acid scavenger refers to a compound that can capture and generate an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amine, tertiary amine and ammonium salt are more preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and alkylamine derivatives having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid scavenger is an anion having a cation selected from the group consisting of ammonium, diazo, iodonium, perium, phosphonium, pyridinium and the like and an acid having a lower acidity than that generated by the acid generator. Salt is preferred.

As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, perium hydroxide having a 2-oxoalkyl group, and specifically Triphenyl perium hydroxide, tris(tert-butylphenyl) perium hydroxide, bis(tert-butylphenyl) iodonium hydroxide, benzalkonium methylthiophenium hydroxide, 2-oxopropane hydroxide base thiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. are mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.

Specific examples of preferable acid scavengers 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 (diazabicyclo undecyl), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylene glycol Amine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine Amine, N,N,N',N'-Tetrabutyl-1,6-hexanediamine, Spermine, Diaminocyclohexane, Bis(2-methoxyethyl)amine, Piperidine , methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane (dianilinoethane), 2-aminoethanol, toluidine, aminophenol, hexylaniline, benzene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrroleidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylamine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger, but when it does contain an acid scavenger, the content of the acid scavenger is usually 0.001 to 10% by mass based on the total solid content of the composition. Preferably it is 0.01-5 mass %.

The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction of the resolution caused by the increase in thickness of the relief pattern with time from exposure to heat treatment. , 300 or less is better. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜Other additives＞ Various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, Antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (eg, defoamer, flame retardant, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 paragraphs 0101 to 0104, paragraphs 0107 to 0109, etc., and these contents are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the photosensitive composition.

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

By including a surfactant in the photosensitive composition, the liquid properties (especially, fluidity) at the time of preparation as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, it is possible to more preferably form a film with a uniform thickness with little thickness unevenness.

Examples of fluorine-based 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 (the above are manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used, and these The contents are incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, which are incorporated into the present specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a compound having 2 or more (preferably 5 The repeating unit of the (meth)acrylate compound of an alkaneoxy group (preferably vinyloxy group, propyleneoxy group) of more than one), the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention . 【Chemical formula 52】

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, which are incorporated into the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.

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

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 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

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, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO., LTD.), etc.

As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products 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 (TAKEMOTO OIL&FAT CO., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.

Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[Higher fatty acid derivatives] In order to prevent the inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the photosensitive composition, so that it is not uniformly present in the drying process after coating on the surface of the photosensitive composition.

In addition, the compound described in the paragraph 0155 of International Publication No. WO 2015/199219 can also be used as the higher fatty acid derivative, and the content is incorporated in the present specification.

When the photosensitive composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive composition. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The photosensitive composition may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, which are incorporated herein by reference.

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

[Inorganic particles] The photosensitive composition may contain inorganic fine particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above-mentioned average particle diameter of the fine particles is a primary particle diameter and a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

[Ultraviolet absorber] The photosensitive composition may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Examples of benzophenone-based ultraviolet absorbers include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 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-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The photosensitive composition may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001 mass % or more and 1 mass % relative to the total solid content mass of the photosensitive composition The following is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

[Organo-titanium compound] The photosensitive composition of the present embodiment may contain an organic titanium compound. Since the photosensitive composition contains an organotitanium compound, a resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.

As the organotitanium compound that can be used, an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the photosensitive composition has excellent storage stability and can obtain a good hardened pattern, and thus a titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.

Among them, as the organotitanium compound, from the viewpoint of exhibiting better chemical resistance, those selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds At least one compound is preferred. In particular, bis(ethylacetate)titanium diisopropoxide, tetrakis(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the resin A. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.

〔Antioxidants〕 The photosensitive composition may contain an antioxidant. By containing an antioxidant as an additive, the elongation property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tert-butyl-6-methyl) phenyl) etc. Examples of commercially available antioxidants include 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 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and the contents are incorporated in the present specification. Moreover, the photosensitive composition may contain a latent antioxidant as needed. As potential antioxidants, compounds in which a site that functions as an antioxidant is protected by a protective group can be mentioned, and are prepared by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant when heated to remove the protecting group. Examples of potential antioxidants include compounds described in International Publication No. WO 2014/021023, International Publication No. 2017/030005, and JP 2017-008219 A, the contents of which are incorporated into the present specification. As a commercial item of a potential antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and formula (3) the indicated compound.

【Chemical formula 53】

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R ⁶ represents an extension of carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group contained in the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

Since it can act on a resin and a metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.

The compounds represented by the general formula (3) include the following as examples, but are not limited to the following structures.

[Chemical formula 54]

【Chemical formula 55】

【Chemical formula 56】

[Chemical formula 57]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the photosensitive composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

[Anti-agglomeration agent] The photosensitive composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

In this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The photosensitive composition may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01 mass % or more and 10 mass % relative to the total solid mass of the photosensitive composition The following is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

[Phenolic compounds] The photosensitive composition of this embodiment may contain a phenolic compound 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, Methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above is the product name, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more. The photosensitive composition may or may not contain the phenolic compound, but when included, the content of the phenolic compound is 0.01 mass % or more and 30 mass % relative to the total solid mass of the photosensitive composition The following is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

[Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The photosensitive composition may or may not contain other polymer compounds, but when included, the content of the other polymer compounds is 0.01 mass % or more relative to the total solid mass of the photosensitive composition. 30 mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

<Characteristics of the photosensitive composition> The viscosity of the photosensitive composition can be adjusted by the solid content concentration of the photosensitive composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferable, 2,000 mm ² /s to 10,000 mm ² /s is more preferable, and 2,500 mm ² /s to 8,000 mm ² /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. If it is 1,000 mm ² /s or more, for example, it is easy to coat with a film thickness required as an interlayer insulating film for rewiring layers, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface morphology can be obtained. .

<Regulations on Substances Contained in Photosensitive Compositions> 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 will be improved. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like are exemplified.

From the viewpoint of insulating properties, the metal content of the photosensitive composition is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

In addition, as a method for reducing the metal impurities accidentally contained in the photosensitive composition, a method of selecting a raw material with a small metal content as a raw material constituting the photosensitive composition; filtering the raw material constituting the photosensitive composition can be mentioned. Filtration; lining the apparatus with Teflon, etc., to carry out distillation under conditions that suppress contamination as much as possible.

Considering the use of the photosensitive composition as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.

As the storage container of the photosensitive composition, a conventionally known storage container can be used. In addition, as the container, in order to suppress the contamination of impurities into the raw material or the photosensitive composition, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of photosensitive composition> The photosensitive composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. For the mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating a tank itself, and the like can be employed. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

In addition, in order to remove foreign matter such as dust and particles in the photosensitive composition, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (High Density Polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm as the first stage and an HDPE filter having a pore diameter of 0.2 μm as the second stage are connected in series. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of 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, and more preferably 0.05 MPa or more and 0.7 MPa or less. Preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after the filtration using a filter, the step of leaving the photosensitive composition filled in the bottle in a reduced pressure state and deaerating may be performed. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Synthesis example: Synthesis of polymer P-1> 13.96 g (0.045 mol) of 4,4'-oxydiphthalic dianhydride (ODPA, the following compound) was dissolved in NMP (NMP) under a stream of dry nitrogen. -methyl-2-pyrrolidone) in 100 g. Thereto were added 1.09 g (0.010 mol) of MAP (the compound described below) and 20 g of NMP. Further, 19.95 g (0.033 mol) of HFHA (the following compound), 6.00 g (0.010 mol) of Jeffamine (registered trademark) ED600, 0.62 g (0.003 mol) of SiDA (the following compound), and 20 g of NMP were added, and the mixture was heated to 60 The reaction was carried out for 1 hour at 180°C, followed by stirring at 180°C for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. After the precipitate was collected by filtration and washed with water three times, it was dried using a vacuum dryer at 50° C. for 72 hours, thereby obtaining a powder of polymer P-1. 【Chemical formula 58】

<Synthesis example: Synthesis of polymer P-2> To a flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was added, and 2,2'-bis(3-amino-4-hydroxyphenyl) was added 13.92 g (38 mmol) of hexafluoropropane were stirred and dissolved. Next, 7.48 g (28 mmol) of dodecanedioyl dichloride and 3.56 g (12 mmol) of 4,4'-diphenyl ether dimethyl chloride were added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C. ), return to room temperature (25°C) and continue stirring for 3 hours. The solution was poured into 3 liters of water, and the precipitate was recovered, washed with pure water three times, and then reduced in pressure to obtain polyhydroxyamide (hereinafter, referred to as P-2). The weight average molecular weight of P-2 was 41,800, and the degree of dispersion was 2.0. The polymer P-2 is a resin of the following structure. In the following description, x:y represents the content ratio (molar ratio) of each repeating unit. 【Chemical formula 59】

<Synthesis example: Synthesis of polymer P-3> 23.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) was dissolved in 3-methoxy-N,N-dimethylpropionamide 13 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dissolved in 3-methoxy-N,N-dimethylpropionamide by dropwise addition to the solution obtained in 190 g 75 g of the obtained solution was stirred at 30° C. for 2 hours to obtain a polyamic acid. To this was added 37 g of trifluoroacetic anhydride at 40° C. or lower, and after stirring at 45° C. for 3 hours, 25.5 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was stirred at 40° C. for 10 hours. The reaction was added dropwise to distilled water three times, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor. Using gel permeation chromatography (GPC), the weight average molecular weight, the number average molecular weight, and the degree of dispersion were determined by standard polystyrene conversion under the following conditions. The weight average molecular weight of polymer P-3 was 20,000, and the degree of dispersion was 1.74. The polymer P-3 is a resin of the following structure. 【Chemical formula 60】

<Synthesis example: Synthesis of polymer P-4> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) were mixed ear) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme. Then, it stirred at the temperature of 60 degreeC for 18 hours, and produced the diester of 4,4'- oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -5°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 2 hours 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 was added dropwise to the reaction mixture over a period of 2 hours. After the reaction mixture was allowed to react at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. 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, stirred again in 4 liters of water for 30 minutes and filtered again. Next, 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 the polymer P-4 (polyimide precursor) was 18,000. The polymer P-4 is a resin of the following structure. [Chemical formula 61]

<Synthesis example: Synthesis of polymer P-5> 7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3',4,4'-biphenyl 6.23 g (25 mmol) of tetracarboxylic dianhydride was added to the reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the heat generation by the reaction was completed, it was cooled to room temperature, and was further left to stand for 16 hours. Next, under ice-cooling, 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 while stirring. middle. Next, a suspension of 9.3 g (46 mmol) of 4,4′-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. Furthermore, after stirring at room temperature for 2 hours, 3 ml of ethanol was added and the mixture was stirred for 1 hour. After that, 100 ml of γ-butyrolactone was added. A reaction liquid was obtained by removing the precipitate generated in the reaction mixture by filtration. The obtained reaction solution was added to 3 liters of ethanol, whereby a precipitate formed of a crude polymer was generated. The resulting crude polymer was collected by filtration 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 a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain a powdery polymer P-5. The weight average molecular weight (Mw) of this polymer was measured, and as a result, it was 23,000. The polymer P-5 is a resin of the following structure. Subscripts in parentheses indicate the molar ratio of each repeating unit. 【Chemical formula 62】

<Examples and Comparative Examples> Compositions 1 to 9 were obtained by mixing the components described in the following tables. The numerical values described in the tables are those expressed by "parts by mass" as the content of each component. The obtained composition was subjected to pressure filtration through a filter made of polytetrafluoroethylene having a filter pore diameter of 0.8 μm. In addition, in the table|surface, the description of "-" means that the corresponding component is not contained.

【Table 1】 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7 Composition 8 Composition 9 resin P-1 - - - - 35 - - - - P-2 - - - 35 - - - - - P-3 - - 33.42 - - - - - - P-4 - - - - - 36.79 30.50 36.80 36.80 P-5 36.79 38.08 - - - - - - - polymeric compound B-1 - - 6.69 - - - 3.05 5.52 5.52 B-2 - - - 1 - - - - - B-3 - - - - 1 - - - - B-4 5.53 5.53 - - - - - - - B-5 - - 5.01 - - 5.53 - - - Sensitizer C-1 - - - - - - - - 0.65 C-2 1.29 - 1.51 - - 1.29 1.37 1.29 0.65 C-3 - - - 5 5 - - - - Metal Adhesion Improver D-1 - - 1 - - - - - - D-2 0.73 0.73 - - - 0.73 0.61 0.74 0.74 migration inhibitor E-1 0.12 0.12 0.33 - - 0.12 0.10 - - E-2 - - - - - - - 0.12 0.12 polymerization inhibitor F-1 0.1 0.1 - - - 0.1 0.10 - - F-2 - - 0.1 - - - - - - F-3 - - - - - - 0.20 0.07 0.07 F-4 - - - - - - 0.08 - - alkali generator G-1 1.03 1.03 - - - 1.03 - - - G-2 - - - - - - 1.03 1.02 1.02 additive H-1 - - 0.14 - - - - - - H-2 - - - 4 4 - - - - H-3 - - - - - - 0.60 - - solvent I-1 - - - 27.99 27.99 43.53 49.89 43.55 43.55 I-2 - - - - - 10.88 12.47 10.89 10.89 I-3 - - - 26.94 26.94 - - - - I-4 - - - 0.07 0.07 - - - - I-5 10.88 10.88 - - - - - - - I-6 43.53 43.53 51.8 - - - - - -

The details of each component described in the table are as follows.

[resin] ·P-1～P-5: P-1～P-5 synthesized as above

[Polymerizable compound] · B-1: SR-209 (manufactured by Sartomer) · B-2: NIKALAC MX-270 (manufactured by Sanwa Chemical Co., Ltd.) ·B-3: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.) ·B-4: Triethylene glycol dimethacrylate ·B-5: A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.

[Photosensitizer] - C-1: Irgacure OXE-01 (manufactured by BASF Corporation) - C-2: Irgacure 784 (manufactured by BASF Corporation) - C-3: A compound of the following structure. 2:1 represents the molar ratio of each structure. [Chemical formula 63]

[Metal Adhesion Improver] D-1: gamma ureidopropyl triethylsilane D-2: N-[3-(triethoxysilyl)propyl]maleic acid (CAS.33525-68-7)

[Migration inhibitor] ·E-1: (5-aminotetrazole) · E-2: Tetrazole

[Polymerization inhibitor] · F-1: 2MeHQ (methoxyhydroquinone) F-2: Tabon (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dicarbonyl) · F-3: PBQ (p-benzoquinone) · F-4: MEHQ (4-methoxyphenol)

[Base generator] G-1: (1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone) G -2: (Compound of the following structure) [Chemical formula 64]

[Additive] · H-1: Compound of the following structure · H-2: Compound of the following structure · H-3: 7-diethylamino-4-methylcoumarin [Chemical formula 65]

[Solvent] I-1: GBL (gamma-butyrolactone) · I-2: DMSO (dimethyl sulfoxide) ·I-3: MDM (diethylene glycol dimethyl ether) I-4: IPA (isopropyl alcohol) ·I-5: EL (ethyl lactate) I-6: NMP (N-methyl-2-pyrrolidone)

[Evaluation] <Preparation method of cured product> The photosensitive layer was formed by applying each photosensitive composition described in the column of "composition" in the following table to a silicon wafer by spin coating. The silicon wafer on which the photosensitive layer was formed was dried at 100° C. for 5 minutes on a hot plate to form a photosensitive film with a uniform thickness described in the column of “film thickness (μm)” in the table on the silicon wafer. sexual layer. In the example of using compositions other than composition 2 as compositions, a strip-shaped sample (3 mm × 30 mm) evaluation mask was placed on the photosensitive layer on the silicon wafer, and 400 mJ/cm ² of ultraviolet rays were irradiated (broadband light). In the example in which a composition other than Composition 5 was used as the composition, the exposed photosensitive layer was developed for 60 seconds using cyclopentanone, and rinsed with PGMEA. In the example using the composition 5 as a composition, the photosensitive layer after exposure was developed using a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution, and rinsed with pure water. Then, using the heating device described in the column of "heating device (wavelength)" in the table, the heating temperature described in the column of "heating temperature" is maintained for the time described in the column of "heating time" to cure , thereby obtaining a hardened resin layer. In the example described as "N ₂ " in the column of "environment" in the table, the heating was performed in a nitrogen atmosphere, and in the example described as "N ₂ +O ₂ (500 ppm)", the heating was performed at 500 ppm including 500 ppm carried out in an oxygen-nitrogen atmosphere. In the example described as IR in the column of "heating device (wavelength)", heating was performed using an infrared lamp heating device RTP-6 manufactured by ADVANCE RIKO, Inc. In the example described as a Box oven in the column of "heating device (wavelength)", the heating was performed using a clean oven CLH-21 manufactured by Koyo Thermo Systems Co., Ltd. The cured resin layer was immersed in a 3 mass % hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a cured product. In the example in which the composition 2 was used as the composition, the exposure and development were not carried out, except that the cured product was heated by the same method to prepare a cured product, and the peeled cured product was cut into strips of 3 mm x 30 mm using a cutter sample.

<Evaluation method of elongation at break> The elongation at break of the obtained hardened|cured material (stripe sample) was measured using the 5960 double-column bench-top tester manufactured by Instron. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "elongation at break" in the table. -Evaluation criteria- A: More than 60%. B: More than 55% and 60% or less. C: More than 50% and 55% or less. D: 50% or less.

<Measuring method of glass transition temperature> The glass transition temperature (Tg) of the obtained hardened|cured material was measured using the Rheogel E4000 by UBM company. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "Tg" in the table. -Evaluation criteria- A: Tg exceeds 250°C. B: Tg exceeds 200°C and is 250°C or lower. C: Tg is 200°C or lower.

<Method for evaluating chemical resistance> The obtained cured product was immersed in a resist stripping solution (MS6310) heated to 75° C. for 15 minutes, washed with running water for 1 minute, and air-dried. Then, the chemical resistance was evaluated based on the change rate (%) of the film thickness before and after the immersion in the above-mentioned resist stripping solution. The above-mentioned change rate (%) is a value represented by the following formula. Change rate (%)=film thickness of cured product after immersion in resist stripping solution (μm)/film thickness of cured product before immersion in resist stripping solution (μm)×100 The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "chemical resistance" in the table. -Evaluation criteria- A: More than 85%. B: More than 75% and 85% or less. C: More than 65% and 75% or less. D: It is 65% or less.

【Table 2】 composition Heating device (wavelength) Thickness (μm) heating time heating temperature environment Elongation at break drug resistance Tg Example 1 Composition 1 IR (780nm～5000nm) 15 0.5h 240 N ₂ B A B Example 2 Composition 3 IR (780nm～5000nm) 15 0.5h 240 N ₂ B B B Example 3 Composition 4 IR (780nm～5000nm) 15 2h 200 N ₂ A B B Example 4 Composition 5 IR (780nm～5000nm) 15 2h 200 N ₂ A B B Example 5 Composition 6 IR (780nm～5000nm) 15 2h 200 N ₂ A A A Example 6 Composition 7 IR (780nm～5000nm) 7 0.5h 240 N ₂ A B A Example 7 Composition 8 IR (780nm～5000nm) 7 0.5h 240 N ₂ A B A Example 8 Composition 9 IR (780nm～5000nm) 15 0.5h 240 N ₂ B B B Example 9 Composition 6 IR (780nm～5000nm) 7 0.5h 240 N ₂ A B A Example 10 Composition 6 IR (780nm～5000nm) 30 0.5h 240 N ₂ B A A Example 11 Composition 6 IR (780nm～5000nm) 15 2h 200 N ₂ A B A Example 12 Composition 6 IR (780nm～5000nm) 15 0.5h 280 N ₂ B A A Example 13 Composition 6 IR (780nm～5000nm) 15 0.5h 240 N ₂ A A A Example 14 Composition 6 IR (780nm～5000nm) 15 0.5h 240 N ₂ +O ₂ (500ppm) A C B Example 15 Composition 1 IR (780nm～5000nm) 15 0.5h 320 N2 B A A Comparative Example 1 Composition 1 Box oven 15 2h 200 N2 D D C Comparative Example 2 Composition 2 IR (780nm～5000nm) 15 2h 200 N2 A D C

From the above results, according to the method for producing a cured product of the present invention, a cured product excellent in chemical resistance can be obtained. In Comparative Example 1, the electromagnetic wave irradiation step was not included, but heating was performed by a box oven. In Comparative Example 2, the composition was not a photosensitive composition. In these comparative examples, it turns out that chemical resistance is inferior.

<Example 101> The above-mentioned composition 1 was applied to the surface of the copper thin layer of the resin substrate having the copper thin layer formed thereon in a layer form by spin coating, and was dried at 100° C. for 300 seconds. The film thickness was set so that the film thickness of the obtained cured product was 5 μm. Then, exposure was performed using a stepper (Nikon Co., Ltd. make, NSR1505 i6). For exposure, via a mask (binary mask with 1:1 line and space pattern, line width 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 120°C for 300 seconds. After the above heating, development was performed using cyclopentanone, followed by rinsing with PGMEA to obtain a layer pattern. Next, using an IR oven (RTP-6 manufactured by ADVANCE RIKO, Inc.), the temperature was increased at a temperature increase rate of 5°C/sec, and after reaching 240°C, the layer was maintained for 30 minutes to harden, thereby forming a rewiring layer. Use an interlayer insulating film. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.

Claims (17)

A method for manufacturing a hardened product, comprising: The film forming step is to apply the photosensitive composition to the substrate to form a photosensitive film; an exposure step, selectively exposing the aforementioned photosensitive film; A developing step develops the photosensitive film after the exposure with a developer to form a pattern; and an electromagnetic wave irradiation step irradiates the pattern obtained by the developing step with electromagnetic waves having a wavelength of 780 nm or more and 5 μm or less. The method for producing a cured product as claimed in claim 1, wherein The photosensitive composition includes at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide imide precursors, epoxy resins and phenol resins. The method for producing a cured product as claimed in claim 1, wherein The photosensitive composition includes at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide precursor. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The said photosensitive composition contains a polymerizable compound. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The aforementioned photosensitive composition contains an organometallic complex as a polymerization initiator. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The glass transition temperature of the obtained cured product exceeded 200°C. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The temperature of the pattern in the aforementioned electromagnetic wave irradiation step is 300° C. or lower. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein In the said electromagnetic wave irradiation process, the total time of the said electromagnetic wave irradiation to a pattern is 60 minutes or less. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The aforementioned electromagnetic wave irradiation step is performed under an inert gas atmosphere. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The aforementioned electromagnetic wave irradiation step is performed in an environment where the oxygen concentration is 1000 ppm or less. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The film thickness of the said photosensitive film is 1 micrometer or more. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The said base material is a base material provided with the metal wiring on the surface on which the photosensitive film is formed. The method for manufacturing a hardened product according to any one of claim 1 to claim 3, wherein The said photosensitive composition contains a photopolymerization initiator or a photoacid generator. A method for manufacturing a layered body, comprising repeating the steps of repeating the method for manufacturing a cured product according to any one of Claims 1 to 13 a plurality of times. The manufacturing method of the laminated body of Claim 14 which further comprises the metal layer formation step of forming a metal layer on the layer formed of the hardened|cured material during the said manufacturing method of the hardened|cured material performed a plurality of times. A method for manufacturing a semiconductor element, comprising the method for manufacturing a cured product according to any one of Claims 1 to 13. A method of manufacturing a semiconductor element, comprising the method of manufacturing a laminate according to claim 14 or claim 15.