TWI767436B - Manufacturing method of laminated body, manufacturing method of semiconductor element, and manufacturing method of rewiring layer - Google Patents

Abstract

The present invention provides a method for producing a laminate having excellent adhesion and a method for producing a semiconductor element, comprising: a step of forming a photosensitive resin composition layer, a step of exposing the photosensitive resin composition layer, and a step of performing a negative development process. step, the step of forming a metal layer on the surface of the photosensitive resin composition layer, and the surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment, further including the following sequence again The photosensitive resin composition layer forming step, the exposure step and the developing treatment step are carried out; the photosensitive resin composition comprises a resin selected from polyimide precursors and the like, and further satisfies that the resin contains a polymerizable group, and the photosensitive resin composition contains At least one of polymerizable compounds.

Description

Manufacturing method of laminated body, manufacturing method of semiconductor element, and manufacturing method of rewiring layer

The present invention relates to a method of manufacturing a laminate and a method of manufacturing a semiconductor element. In particular, it relates to a method for producing a laminate used for producing an interlayer insulating film for a rewiring layer of a semiconductor element.

Thermosetting resins such as polyimide resins and polybenzoxazole resins are used for insulating layers of semiconductor elements and the like because they are excellent in heat resistance and insulating properties. In addition, polyimide resin or polybenzoxazole resin is also in the state of the precursor before the cyclization reaction (polyimide precursor or polybenzoxazole precursor) because of its low solubility in solvents. It is used, and after being applied to a substrate or the like, it is heated to cyclize the polyimide precursor to form a cured film.

Here, Patent Document 1 discloses a laminate including a thermoplastic polyimide layer and a metal layer on the surface of the thermoplastic polyimide layer. In addition, Patent Document 1 also describes that the thermoplastic polyimide layer functions as an insulating layer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication WO2004/050352

[The problem to be solved by the invention] Here, if the thermoplastic polyimide resin described in Patent Document 1 is used as an interlayer insulating film for a rewiring layer of a semiconductor element, it is necessary to include a thermoplastic polyimide layer and a thermoplastic polyimide layer. A thermoplastic polyimide layer is further provided on the laminate of the metal layers on the surface of the amine layer. However, as a result of examining further providing a thermoplastic polyimide layer on the laminate of Patent Document 1, it was found that the adhesion between the thermoplastic polyimide layer and the metal layer, or the thermoplastic polyimide layers is not good. full. An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing a laminate having excellent adhesion between a resin layer and a resin layer, or a resin layer and a metal layer, including a resin such as polyimide, and a method including the The manufacturing method of the semiconductor element of the said manufacturing method.

[MEANS TO SOLVE THE PROBLEM] Based on the said subject, the present inventors made research, and as a result found that the said subject can be solved by performing negative image development on a photosensitive resin composition to form a resin layer. Specifically, the above-mentioned problems are solved by the following means <1>, preferably by means of <2> to <8>. <1> A method for producing a layered product, comprising: a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer; and an exposing step of exposing the photosensitive resin composition layer to light ; developing treatment step, carrying out negative development treatment on the exposed photosensitive resin composition layer; metal layer forming step, forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment; and surface active The chemical treatment step includes subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment, and further includes performing the photosensitive resin composition layer forming step, the exposing step, and In the developing treatment step, the photosensitive resin composition comprises a resin selected from the group consisting of polyimide precursors, polyimide precursors, polybenzoxazole precursors and polybenzoxazoles, so as to satisfy the resin requirements It contains a polymerizable group, and the said photosensitive resin composition contains at least one of a polymerizable compound. <2> The said photosensitive resin composition layer formation process, the said exposure process, and the said image development process process are performed 3 to 7 times in the following order, The manufacturing method of the laminated body of <1>. <3> The method for producing a laminate according to <1> or <2>, wherein the metal layer contains copper. <4> The method for producing a laminate according to any one of <1> to <3>, wherein the resin is a polyimide precursor or a polybenzoxazole precursor. <5> The method for producing a laminate according to any one of <1> to <4>, wherein the resin includes a partial structure represented by -Ar-L-Ar-; wherein Ar is each independently Aromatic group, L is an aliphatic hydrocarbon group containing 1 to 10 carbon atoms that may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or two of the above The basis for the combination of the above. <6> The method for producing a layered body according to any one of <1> to <5>, wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment. <7> The manufacturing method of the layered body according to any one of <1> to <6>, wherein the photosensitive resin composition contains a photopolymerization initiator. <8> A method of manufacturing a semiconductor element including the method of manufacturing a laminate according to any one of <1> to <7>.

[Effect of invention] The present invention provides a method for producing a laminate having excellent adhesion between a resin layer and a resin layer, or a resin layer and a metal layer, and a method for producing a semiconductor element including the method.

The description of the constituent elements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the expression of the group (atomic group) in the present specification, the expression not describing substituted and unsubstituted includes a group without a substituent, and also includes a group with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, as light used for exposure, light such as bright-line spectrum of mercury lamp, far-ultraviolet typified by excimer laser, extreme ultraviolet (Extreme Ultraviolet (EUV) light), X-ray, and electron beam are generally mentioned. chemical radiation or radiation. In this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)allyl" means "allyl" and Both or either of "methallyl", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", "(meth)acryloyl" " represents both or either of "acryloyl" and "methacryloyl". In this specification, the term "step" not only represents an independent step, but also includes in this term as long as the intended function of the step is achieved even if it cannot be clearly distinguished from other steps. In this specification, the solid content concentration refers to the mass percentage of other components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration refers to the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). . In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Co., Ltd.), and combining guard column HZ-L, TSKgel Super HZM -M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Co., Ltd.) were used for the determination of the column. Unless otherwise stated, the elution solution was measured using tetrahydrofuran (THF). In addition, unless otherwise stated, the detection was performed using a detector with a wavelength of 254 nm of ultraviolet rays (UV (ultraviolet) rays).

The method for producing a layered product of the present invention is characterized by including a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layered photosensitive resin composition layer, and exposing the photosensitive resin composition layer to light. step, a development treatment step of performing negative development treatment on the exposed photosensitive resin composition layer, a metal layer formation step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment, and The surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment further includes performing the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step; the photosensitive resin composition comprises a resin selected from polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, and further satisfies the The resin contains a polymerizable group, and the photosensitive resin composition contains at least one of a polymerizable compound. In this way, when the insulating film is laminated, the negative-tone development is performed, and further the surface activation treatment is performed, whereby the adhesion between the layers can be improved. On the other hand, in the said patent document 1, there is no example which laminated|stacked such a resin layer. Moreover, in patent document 1, since positive image development is performed and the exposed part is subjected to alkali development, the adhesiveness tends to become insufficient. Furthermore, in the case of positive development, the unexposed portion of the resin layer is subjected to surface activation treatment, and it is presumed that the photosensitive resin composition layer (resin layer) is easily damaged, resulting in a decrease in adhesiveness. On the other hand, in the negative type, a three-dimensional cross-linked structure can be formed, the strength of the film can be increased, and the surface activation treatment can hardly be damaged. Based on the above, in the present invention, by adopting the above-mentioned means, even if it is a multilayer structure, high adhesion between the resin layer and the resin layer, and between the resin layer and the metal layer can be achieved. Hereinafter, the details of the present invention will be described.

<Photosensitive resin composition layer forming step> The manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process of applying a photosensitive resin composition to a board|substrate and forming it into a layer. As means for applying the photosensitive resin composition to the substrate, coating is preferred. Specifically, as the means to be applied, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, and spin coating can be exemplified. method, slit scanning method and inkjet method. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, the spin coating method is more preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 rpm to 2000 rpm for about 10 seconds to 1 minute. The thickness of the photosensitive resin composition layer (resin layer) is preferably applied so as to be 0.1 μm to 100 μm after exposure, and more preferably applied so as to be 1 μm to 50 μm. In addition, as shown in FIG. 2 mentioned later, the thickness of the photosensitive resin composition layer formed does not necessarily need to be uniform. In particular, when a photosensitive resin composition layer is provided on a surface having unevenness, as shown in FIG. 2 , it may become a resin layer with different thicknesses. In particular, when a plurality of layers are stacked, deep concave portions are formed as concave portions, but the present invention has a high technical value for such a configuration in that the peeling between layers can be suppressed more effectively. In addition, when the laminated body of this invention has resin layers with different thicknesses, it is preferable that the thickness of the resin layer of the thinnest part is the said thickness. The type of substrate can be appropriately determined according to the application, such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon and other semiconductor substrates, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, Ni, Metal substrates such as Cu, Cr, Fe, paper, Spin On Glass (SOG), Thin Film Transistor (TFT) array substrates, electrode plates for Plasma Display Panel (PDP), etc. , without special restrictions. In the present invention, a semiconductor fabrication substrate is particularly preferred, and silicon is more preferred. Moreover, when a photosensitive resin composition layer is formed on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate. Details of the photosensitive resin composition will be described below.

<Filtering step> The manufacturing method of the laminated body of this invention may also include the process of filtering the photosensitive resin composition before applying the photosensitive resin composition to a board|substrate. Filtration is preferably performed using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. The filter can also be washed with an organic solvent in advance. In the filter filtering step, a plurality of filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can also be used in combination. In addition, various materials may be filtered multiple times, and the multiple filtering steps may also be cyclic filtering steps. In addition, filtration may be performed by pressurization, and the pressure of pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, an adsorption material may be used to remove impurities, or a combination of filter filtration and an adsorption material may be used. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.

<Drying step> The manufacturing method of the laminated body of this invention may include the process of drying a solvent after forming the photosensitive resin composition layer. The preferable drying temperature is 50°C to 150°C, more preferably 70°C to 130°C, and still more preferably 90°C to 110°C. As a drying time, 30 second - 20 minutes can be illustrated, More preferably, it is 1 minute - 10 minutes, More preferably, it is 3 minutes - 7 minutes.

<Exposure process> The manufacturing method of the laminated body of this invention includes the exposure process which exposes the said photosensitive resin composition layer. The exposure is not particularly limited as long as the photosensitive resin composition can be cured. For example, in terms of exposure energy at a wavelength of 365 nm, the exposure is preferably 100 mJ/cm ² to 10,000 mJ/cm ² , more preferably 200 mJ. /cm ² ～8000 mJ/cm ² . The exposure wavelength can be appropriately determined in the range of 190 nm to 1000 nm, and is preferably 240 nm to 550 nm.

<Development process step> The manufacturing method of the layered product of the present invention includes a development treatment step of subjecting the exposed photosensitive resin composition layer to a negative development treatment. Unexposed parts (non-exposed parts) are removed by performing negative development. The development is performed using a developer. The developing solution can be used without particular limitation as long as it can remove the unexposed part (non-exposed part). The solvent is preferably: as esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyl acetate, etc. ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, ε-caprolactone, delta-valerolactone, alkyl alkoxyacetates (e.g. methyl alkoxyacetate) , ethyl alkoxyacetate, butyl alkoxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.)), 3-alkoxy propionate alkyl esters (such as 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc. (such as 3-methoxy propionate methyl ester, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (such as 2-alkoxypropionate) Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methylpropionate propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy- Ethyl 2-methylpropionate (such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate Esters, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, two Ethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example Preferable examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as the aromatic hydrocarbons, for example, suitable Toluene, xylene, anisole, limonene, etc. are listed, and as the sulfites, dimethylsulfite, ethyl carbitol acetate, and butyl carbitol acetate can be suitably used. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, ethyl butyl carbitol acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate, more preferably cyclopentanone and γ-butyrolactone. The development time is preferably 10 seconds to 5 minutes. The temperature at the time of image development is not specifically limited, Usually, it can carry out at 20 degreeC - 40 degreeC. After the treatment using the developer, further rinsing may be performed. Rinse is preferably performed with a solvent different from that of the developer. For example, rinsing can be performed using the solvent contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<Heating step> It is preferable that the manufacturing method of the laminated body of this invention includes a heating process. In the heating step, a cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is performed. When heated with a crosslinking agent, a three-dimensional network structure is formed in the polyimide or polybenzoxazole. Moreover, hardening etc. of the unreacted radically polymerizable compound are also performed. The maximum heating temperature is preferably 100°C to 500°C, more preferably 140°C to 400°C, and still more preferably 160°C to 350°C. Heating is preferably carried out from a temperature of 20°C to 150°C to a maximum heating temperature at a temperature increase rate of 1°C/min to 12°C/min, more preferably 2°C/min to 10°C/min, further preferably 3 °C/min to 10 °C/min. By setting the temperature increase rate to be 1°C/min or more, productivity can be ensured and excessive volatilization of the amine can be prevented, and by setting the temperature increase rate to be 12°C/min or less, the residual stress of the cured film can be relieved. The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the step of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied to a substrate and then dried, it refers to the temperature after drying, and is preferably 30° C. to 200° C. lower than the boiling point of the solvent contained in the photosensitive resin composition, for example. ℃ temperature gradually increased. About heating, after reaching the maximum heating temperature, heating is preferably performed for 10 minutes to 360 minutes, more preferably heating for 20 minutes to 300 minutes, and particularly preferably heating for 30 minutes to 240 minutes.

Heating can also be performed in stages. As an example, the following steps can be mentioned: the temperature is raised from 25°C to 180°C at 3°C/min, left at 180°C for 60 minutes, then the temperature is raised from 180°C to 200°C at 2°C/min, and the temperature is increased to 200°C at 200°C. 120 minutes at ℃. Further, cooling may be performed after heating, and the cooling rate at this time is preferably 1°C/min to 5°C/min.

From the viewpoint of preventing decomposition of the polyimide precursor and the like, the heating step is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm (v/v) or less, more preferably 20 ppm (v/v) or less.

<<Metal Layer Formation Step>> It is preferable that the manufacturing method of the laminated body of this invention includes the metal layer formation process of forming a metal layer on the surface of the photosensitive resin composition layer after image development processing. The metal layer is not particularly limited, and existing metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper. The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, methods of combining these, and the like are contemplated. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating are exemplified. The thickness of the metal layer is preferably from 0.1 μm to 50 μm, more preferably from 1 μm to 10 μm, at the thickest part.

<Surface activation treatment step> The manufacturing method of the layered product of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, and the metal layer formation step may be performed after the surface activation treatment step for the photosensitive resin composition layer after the exposure and development step. The surface activation treatment may be performed only on at least a part of the metal layer, only on at least a part of the photosensitive resin composition layer after exposure, or on both the metal layer and the photosensitive resin composition layer after exposure. at least part of it. The surface activation treatment is preferably performed on at least a part of the metal layer, and more preferably, a surface activation treatment is performed on a part or all of a region of the metal layer in which the photosensitive resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin layer 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 photosensitive resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion to the metal layer or resin layer provided on the surface activation treatment surface can be improved. In particular, when positive-type development is performed, the unexposed portion is subjected to surface activation treatment, and the photosensitive resin composition layer (resin layer) is easily damaged, resulting in a decrease in adhesiveness. In the present invention, since the negative tone development is performed, the exposed portion is subjected to surface treatment, and the strength of the film is improved by curing or the like, so that the photosensitive resin composition layer (resin layer) is not damaged, and this problem does not exist. Specifically, the surface activation treatment can be selected from plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.); corona discharge treatment; Etching treatment by CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ ; Surface treatment by ultraviolet (UV) ozone method; After removal, immersion treatment in an organic surface treatment agent containing at least one compound of an amine group and a thiol group; in the mechanical roughening treatment using a brush, plasma treatment is preferred, and a raw material is particularly preferred Oxygen plasma treatment using oxygen in the gas. In the case of corona discharge treatment, the energy is preferably 500 J/m ² to 200,000 J/m ² , more preferably 1000 J/m ² to 100,000 J/m ² , and most preferably 10,000 J/m ² to 50,000 J/m ² .

<Lamination step> The manufacturing method of the present invention further includes the following lamination steps. The lamination step is a series of steps including the step of forming the photosensitive resin composition layer, the exposure step, and the development treatment step in the following order again. That is, in the lamination step, of course, the drying step, the heating step, and the like may be further included. When the lamination process is performed after the lamination process, the surface activation treatment process is preferably performed after the exposure process or after the metal layer formation process. The lamination step is preferably performed 3 to 7 times, more preferably 3 to 5 times. For example, resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer are preferably composed of 3 or more and 7 or less layers, and more preferably 3 or less and 5 or less layers. If it is two or less layers, it may be sufficiently adhered even without oxygen plasma treatment or the like, and the more the multilayer structure is, the more repeated exposure to developing solution, metal etching treatment, and high-temperature treatment of curing becomes easier. Peeling occurs at the metal layer/resin layer interface or the resin layer/resin layer interface. By setting it as such a structure, a photosensitive resin composition layer (resin layer) and a metal layer can be laminated|stacked alternately, and it can be used as a multilayer wiring structure of a semiconductor.

<Photosensitive resin composition> The photosensitive resin composition used in the present invention (hereinafter, sometimes referred to as "the composition used in the present invention") contains a polyimide precursor selected from the group consisting of polyimide precursors, polyimide, polyimide Resin in benzoxazole precursor and polybenzoxazole (hereinafter, sometimes referred to as "polyimide precursor"), preferably including polyimide precursor or polybenzoxazole precursor , more preferably including a polyimide precursor. Furthermore, it satisfies that resin such as a polyimide precursor contains a polymerizable group, and the photosensitive resin composition contains at least one of a polymerizable compound. In particular, it is preferable that a resin such as a polyimide precursor contains a polymerizable group, and the photosensitive resin composition contains a polymerizable compound. By setting it as such a structure, a three-dimensional network is formed in the exposure part to form a strong cross-linked film, and the photosensitive resin composition layer (resin layer) is not damaged by the surface activation treatment, and the surface activation Handling and adhesion are improved more effectively. Furthermore, it is preferable that resins, such as a polyimide precursor, contain the partial structure represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group (preferably an alkylene group) containing 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, A group of -SO ₂ - or -NHCO-, or a combination of two or more of the above. By setting it as such a structure, a resin layer becomes a soft structure, and the effect of suppressing generation|occurrence|production of peeling can be exhibited more effectively. Ar is preferably 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. Hereinafter, the details of the photosensitive resin composition used in the present invention will be described.

式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示二價的有機基，R¹¹⁵ 表示四價的有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或一價的有機基。<<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). Formula (2) [Chemical 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 a hydrogen atom or Monovalent organic group.

A ¹ and A ² in 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, a group including a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group can be exemplified, and a linear or branched aliphatic group having 2 to 20 carbon atoms is preferred. , a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, more preferably a group containing an aromatic group having 6 to 60 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group containing 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- , or the combination of two or more of the above. The preferred ranges of these are as described above.

R ¹¹¹ is preferably 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, it is preferable to contain a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. The diamine of the combined group is more preferably a diamine containing a group containing an aromatic group having 6 to 60 carbon atoms. As an example of an aromatic group, the following are mentioned.

式中，A較佳為單鍵、或選自可經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C(=O)-、-S-、-S(=O)₂ -及-NHCO-、以及該些的組合中的基，更佳為單鍵、選自可經氟原子取代的碳數1～3的伸烷基、-O-、-C(=O)-、-S-、-SO₂ -中的基，進而佳為選自由-CH₂ -、-O-、-S-、-SO₂ -、-C(CF₃ )₂ -及-C(CH₃ )₂ -所組成的群組中的二價的基。[hua 2]

In the formula, A is preferably a single bond, or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O ) ₂ - and -NHCO-, and the group in the combination of these, more preferably a single bond, selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O )-, -S-, -SO ₂ -, and preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C( CH ₃ ) ₂ - a divalent radical in the group consisting of.

Specifically, as the diamine, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminopropane, 4-Diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane , 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane Hexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino -3,3'-Dimethylcyclohexylmethane 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'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3 '-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2 -Bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2 2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4 -Hydroxyphenyl) hexafluoropropane, bis(3-amino-4-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-terphenyl , 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] bis[4-(3-aminophenoxy) Phenyl] benzene, bis[4-(2-aminophenoxy)phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminobenzene) base) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3- Aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'- Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3 ,3-Dihydroxy-4,4'-diamine Biphenyl, 9,9'-bis(4-aminophenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5 '-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenedi Amine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyl disiloxane, 2,7-diaminophenanyl, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, diamine Esters of benzoic 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 , 2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

Moreover, the diamine (DA-1) - diamine (DA-18) shown below are also preferable.

[hua 3]

[hua 4]

Moreover, the diamine which has at least two or more alkanediol units in a main chain can also be mentioned as a preferable example. A diamine containing either or both of two or more ethylene glycol chains and propylene glycol chains in one molecule is preferable, and a diamine not containing an aromatic ring is more preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, and Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 ( The above are trade names, Huntsman (HUNTSMAN) Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1- (1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine and the like, but are not limited to these specific examples. Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED -2003 The structures of Jeffamine (registered trademark) EDR-148 and Jeffamine (registered trademark) EDR-176 are shown below.

[hua 5]

In the above, x, y, and z are mean values.

From the viewpoint of the flexibility of the obtained cured 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 (preferably an alkylene group) containing 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, A group of -SO ₂ - or -NHCO-, or a combination of two or more of the above. Ar is preferably a phenylene group, and L is further 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.

（51） 式（51）中，R¹⁰ ～R¹⁷ 分別獨立地為氫原子、氟原子或一價的有機基，R¹⁰ ～R¹⁷ 的至少一個為氟原子、甲基或三氟甲基。 作為R¹⁰ ～R¹⁷ 的一價的有機基，可列舉碳數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。 式（61） [化7]

（61） 式（61）中，R¹⁸ 及R¹⁹ 分別獨立地為氟原子或三氟甲基。 作為具有式（51）或式（61）的結構的二胺化合物，可列舉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。該些可使用一種，亦可組合兩種以上而使用。In addition, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-ray transmittance and easiness of acquisition, a divalent organic group represented by formula (61) is more preferable. Formula (51) [Chem. 6]

(51) In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), carbon atoms of 1 to 10 (preferably carbon atoms of 1). ~6) fluorinated alkyl groups, etc. Equation (61) [Chem. 7]

(61) In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group. As the diamine compound having 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. One of these may be used, or two or more of them may be used in combination.

式（5）中，R¹¹² 較佳為單鍵、或選自可經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -及-NHCO-、以及該些的組合中的基，更佳為單鍵、選自可經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中的基，進而佳為選自由-CH₂ -、-C(CF₃ )₂ -、-C(CH₃ )₂ -、-O-、-CO-、-S-及-SO₂ -所組成的群組中的二價的基。R ¹¹⁵ in formula (2) represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6). Formula (5) [Chemical 8]

In formula (5), R ¹¹² is preferably a single bond, or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO- and the group in the combination thereof, more preferably a single bond, selected from the group consisting of alkylene having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and - The group in SO ₂ - is more preferably selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ - a bivalent base in the group formed.

Formula (6) [Chemical 9]

（O） 式（O）中，R¹¹⁵ 表示四價的有機基。R¹¹⁵ 與式（2）中的R¹¹⁵ 為相同含義，較佳的範圍亦相同。Specific examples of R ¹¹⁵ include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical 10]

(O) In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as 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'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetra Carboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3 ',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3, 3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4, 9,10-Perylenetetracarboxylic dianhydride, 1,2,4,5-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-Naphthalenetetracarboxylic dianhydride, 1,8,9,10-Phenanthrene Tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2, 3,4-benzenetetracarboxylic dianhydride, and these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, the tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below can also be mentioned as a preferable example. [Chemical 11]

Moreover, it is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, more preferably both of them contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and is preferably a photoradical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an oxymethyl group, an epoxy group, an oxetanyl group, and a benzoxazole. Lino group, blocked isocyanate group, methylol group, amine group. As a radical polymerizable group which a polyimide precursor etc. have, the group which has an ethylenically unsaturated bond is preferable. As a group which has an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, the group represented by following formula (III), etc. are mentioned.

[Chemical 12]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, more preferably a methyl group. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecylene, -CH ₂ CH(OH)CH ₂ -, more preferably ethylidene, propylidene, trimethylene, -CH ₂ CH(OH)CH ₂ -. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylidene group.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group includes an aromatic group, an aralkyl group, and the like having one, two, or three, preferably one, acidic group bonded to carbon constituting the aryl group. Specifically, an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group can be mentioned. More specifically, the phenyl group which has an acidic group and the benzyl group which has an acidic group are mentioned. The acidic group is preferably an OH group. R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The number of carbon atoms in the alkyl group is preferably from 1 to 30. The alkyl group may be any of straight chain, branched and cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy) Ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethoxy)ethyl) oxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, and camphenyl , dicyclohexyl and pinenyl. Among them, a cyclohexyl group is the most preferable from the viewpoint of coexisting with high sensitivity. Moreover, as the alkyl group substituted with an aromatic group, the straight-chain alkyl group substituted with the aromatic group mentioned later is preferable. Specific examples of the aromatic group include: substituted or unsubstituted benzene ring, naphthalene ring, pentavine ring, indene ring, azulene ring, heptavine ring, indene ring, perylene ring, condensed pentabenzene ring , acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, triphenylene ring, perylene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole Ring, Thiazole Ring, Pyridine Ring, Pyrazine Ring, Pyrimidine Ring, Pyridazine Ring, Indolizine Ring, Indole Ring, Benzofuran Ring, Benzothiophene Ring, Isobenzofuran Ring, Quinazine Ring, Quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acridine ring, phenanthrene ring, thianthrene ring, benzopyran ring, xanthene ring, phenothiazine, phenothiazine, or phenazine. The best is a benzene ring.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a counter salt 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 addition, the polyimide precursor also preferably has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less.

In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示二價的有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或一價的有機基，R¹¹³ 及R¹¹⁴ 的至少一者為包含聚合性基的基，較佳為兩者為聚合性基。The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursor and the like used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting it as such a structure, the range of exposure latitude can be further expanded. Formula (2-A) [Chemical 13]

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 preferably both are a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ independently have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and their 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 structural unit represented by the 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, the polyimide precursor may, of course, contain other types of repeating structural units in addition to the repeating unit of the formula (2).

As an embodiment of the polyimide precursor in the present invention, 50 mol % or more, further 70 mol % or more, especially 90 mol % or more of all repeating units are represented by the formula (2). Polyimide precursors for repeating units.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. The degree of dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and still more preferably 2.8 or more. The upper limit value of the degree of dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, still more preferably 3.2 or less, and still more preferably 3.1 or less , more preferably 3.0 or less, and particularly preferably 2.95 or less.

式（4）中，R¹³¹ 表示二價的有機基，R¹³² 表示四價的有機基。 當具有聚合性基時，聚合性基可位於R¹³¹ 及R¹³² 的至少一者中，亦可如下述式（4-1）或式（4-2）所示般位於聚醯亞胺的末端。 （式4-1） [化15]

式（4-1）中，R¹³³ 為聚合性基，其他基與式（4）為相同含義。 （式4-2） [化16]

R¹³⁴ 及R¹³⁵ 的至少一者為聚合性基，當不為聚合性基時為有機基，其他基與式（4）為相同含義。<<Polyimide>> The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imine ring, but is preferably a compound represented by the following formula (4) , more preferably a compound represented by formula (4) and having a polymerizable group. Formula (4) [Chemical 14]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group may be located in at least one of R ¹³¹ and R ¹³² , or may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2). . (Formula 4-1) [Chemical 15]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meaning as in formula (4). (Formula 4-2) [Chemical 16]

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

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group contained in the polyimide precursor or the like. R ¹³¹ represents a divalent organic group. As a divalent organic group, the same thing as R ¹¹¹ in formula (2) can be illustrated, and the preferable range is also the same. In addition, as R ¹³¹ , a diamine residue remaining after removal of the amine group of the diamine can be mentioned. As the diamine, an aliphatic, cycloaliphatic or aromatic diamine etc. are mentioned. As a specific example, the example of ^R111 in Formula (2) of a polyimide precursor can be mentioned.

R ¹³¹ is preferably a diamine residue having at least two or more alkanediol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during calcination. More preferably, it is a diamine residue containing any one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, and even more preferably, it is a diamine residue that does not contain an aromatic ring.

As a diamine containing either or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, Jeffamine (registered trademark) KH-511, Jeffamine (Jeffamine) can be mentioned. ) (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR-148, Jeffamine (Jeffamine) (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by Huntsman Co., Ltd.), 1-(2-( 2-(2-Aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy ) propane-2-amine, etc., but not limited to these diamines.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the same thing as R ¹¹⁵ in formula (2) can be illustrated, and the preferable range is also the same. For example, four bonding groups of the tetravalent organic group exemplified by R ¹¹⁵ are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring. [Chemical 17]

Moreover, the tetracarboxylic-acid residue etc. which remain after removing an anhydride group from a tetracarboxylic dianhydride are mentioned as ^R132 . As a specific example, the example of ^R115 in Formula (2) of a polyimide precursor can be mentioned. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having one to four aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, R ¹³¹ includes 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane , 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the (DA-1)～( DA-18) As a preferable example, as ^R132 , the said (DAA-1) - (DAA-5) are mentioned as a preferable example.

Moreover, it is also preferable that polyimide has a fluorine atom in a structural unit. The fluorine atom content in the polyimide is preferably 10% by mass or more, and is 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 can also be copolymerized with polyimide. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

In addition, in order to improve the storage stability of the composition, the polyimide is preferably a main chain end capped with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, and a monoactive ester compound. Among these, it is more preferable to use a monoamine. Preferable monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amine naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amine naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-amine Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid 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-aminothiophene, 3-aminothiophene, 4-aminothiophene, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

The polyimide is preferably 85% or more, more preferably 90% or more. When the imidization rate is 85% or more, the film shrinkage due to ring closure caused by the imidization by heating is reduced, and the occurrence of warpage can be suppressed.

In addition to all the repeating structural units of the formula (4) based on one R ¹³¹ or R ¹³² , the polyimide may also contain two or more different kinds of repeating units based on these groups. In addition, the polyimide may contain other kinds of repeating structural units in addition to the repeating unit of the formula (4).

The polyimide can be, for example, a method of completely imidizing a polyimide precursor using a known imidization reaction method, or a method of stopping the imidization reaction in the middle and introducing a part of the imide structure. , and then synthesize by incorporating a fully imidized polymer and the polyimide precursor to introduce a part of the imide structure, and the polyimide precursor is obtained by using the following method: A method of reacting a tetracarboxylic dianhydride with a diamine compound (a part of which is substituted with a capping agent as a monoamine) at a low temperature; a method of reacting a tetracarboxylic dianhydride (a part of which is substituted with an acid anhydride or monochloride) at a low temperature A method of reacting a compound or a monoactive ester compound with a diamine compound; a diester is obtained by using a tetracarboxylic dianhydride and an alcohol, which is subsequently replaced with a diamine (a part of which is substituted with an alcohol) in the presence of a condensing agent. A method of reacting as a monoamine end-capping agent); a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is chlorinated with diamine (a part of which is replaced as a monoamine) amine end-capping agent), a method of reacting, etc.

Examples of commercially available polyimide include Durimide (registered trademark) 284 (manufactured by Fujifilm Co., Ltd.), Matrimid 5218 (HUNTSMAN). ) (shares) manufacturing).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. The bending resistance of the film after hardening can be improved by making a weight average molecular weight into 5,000 or more. In order to obtain a cured film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one polyimide is in the above-mentioned range.

<<Polybenzoxazole precursor>>

The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferably represented by the following formula (3).

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 their 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. The aliphatic group is preferably a linear aliphatic group. 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, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable. The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a linear or branched (preferably linear) dicarboxylic acid. Dicarboxylic acid with aliphatic group and two COOH. 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, further preferably 4 to 15, particularly preferably 5 to 10. 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, butanedioic 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 19]

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

As a dicarboxylic acid containing an aromatic group, the dicarboxylic acid which has the following aromatic group is preferable, and the dicarboxylic acid which contains only the following aromatic group and two COOH is more preferable.

式中，A表示選自由-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C(CF₃ )₂ -及-C(CH₃ )₂ -所組成的群組中的二價的基。[hua 20]

In the formula, A represents selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ - Divalent bases in the group consisting of.

As a specific example of the dicarboxylic acid containing an aromatic group, 4,4'- carbonyl dibenzoic acid, 4,4'- dicarboxydiphenyl ether, and terephthalic acid are mentioned.

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-mentioned formula (2), and the preferable range is also the same. In addition, R ¹²² is preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxyl Biphenyl, 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)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amine yl-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-diamine base-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

式中，X₁ 表示-O-、-S-、-C(CF₃ )₂ -、-CH₂ -、-SO₂ -、-NHCO-。[Chemical 21]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, and -NHCO-.

（A-s）[Chemical 22]

(As)

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

（A-sc） （式（A-sc）中，*表示鍵結於由所述式（A-s）所表示的雙胺基苯酚衍生物的胺基苯酚基的芳香環上）[Chemical 23]

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

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

In addition, in the formula (As), R ₂ is an alkyl group and R ₃ is an alkyl group, so that 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 in R ₁ include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ )(CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -CH(CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₃ )-, -C( _CH3 )( _CH2CH2CH2CH3 )-, -CH(CH2CH( _{CH3 )2 )} -, _-C ( _{CH3 ) (} CH2CH( _{CH3 ) 2} )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, etc., in which it is possible to maintain high transparency to i-rays and high levels of hardening at low temperatures In terms of the effect of the cyclization rate and the polybenzoxazole precursor having sufficient solubility in the solvent and excellent balance, -CH ₂ -, -CH(CH ₃ )-, -C( CH ₃ ) ₂ -.

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

Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Laid-Open No. 2013-256506. The contents are incorporated into this specification. Of course, it is not limited to these specific examples.

In addition to the repeating unit of the formula (3), the polybenzoxazole precursor may also contain other types of repeating structural units. It is preferable to contain the diamine residue represented by following formula (SL) as another kind of repeating structural unit from the point which can suppress the generation|occurence|production of the warpage accompanying ring closure.

式（SL）中，Z具有a結構與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 中的至少一者為芳香族基，剩餘為氫原子或碳數1～30的有機基，分別可相同，亦可不同。a結構及b結構的聚合可為嵌段聚合亦可為無規聚合。Z部分的莫耳%中，a結構為5莫耳%～95莫耳%，b結構為95莫耳%～5莫耳%，且a+b為100莫耳%。[Chemical 24]

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 remainder is 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 either block polymerization or random polymerization. In the mol % of the Z part, the a structure is 5 mol % to 95 mol %, the b structure is 95 mol % 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, 400-4,000 are preferable, and, as for the molecular weight of the structure represented by formula (SL), 500-3,000 are more preferable. By setting the molecular weight in the above range, the effect of reducing the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor to suppress the warpage and the effect of improving the solubility of the solvent can be combined more effectively.

When the diamine residue represented by the formula (SL) is included as another kind of repeating structural unit, it is also preferable to include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating structure unit. As an example of such a tetracarboxylic-acid residue, the example of ^R115 in Formula (2) is mentioned.

For example, when used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, and still more preferably 2.2 the following.

式（X）中，R¹³³ 表示二價的有機基，R¹³⁴ 表示四價的有機基。 當具有聚合性基時，聚合性基可位於R¹³³ 及R¹³⁴ 的至少一者中，亦可如下述式（X-1）或式（X-2）所示般位於聚苯并噁唑的末端。 式（X-1） [化26]

式（X-1）中，R¹³⁵ 及R¹³⁶ 的至少一者為聚合性基，當不為聚合性基時為有機基，其他基與式（X）為相同含義。 式（X-2） [化27]

式（X-2）中，R¹³⁷ 為聚合性基，除此以外為取代基，其他基與式（X）為相同含義。<<Polybenzoxazole>> The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), more preferably Preferably, it is a compound represented by the following formula (X) and having a polymerizable group. [Chemical 25]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group may be located in at least one of R ¹³³ and R ¹³⁴ , or may be located in the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). end. Formula (X-1) [Chemical 26]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (X). Formula (X-2) [Chemical 27]

In formula (X-2), R ¹³⁷ is a polymerizable group, other than that, it is a substituent, and other groups have the same meaning as in formula (X).

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group contained in the polyimide precursor or the like.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic or aromatic group is mentioned. As a specific example, the example of ^R121 in Formula (3) of a polybenzoxazole precursor is mentioned. In addition, its preferable example is the same as that of R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in the formula (3) of the polybenzoxazole precursor. In addition, its preferable example is the same as R ¹²² . For example, the four bonding groups of the tetravalent organic group exemplified by R ¹²² are bonded to the nitrogen atom and the oxygen atom in the formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical 28]

The polybenzoxazole preferably has an oxazole rate of 85% or more, more preferably 90% or more. When the oxazolylization ratio is 85% or more, film shrinkage due to ring closure caused by oxazolylization by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

In addition to the repeating structural units of the formula (X) all based on one R ¹³¹ or R ¹³² , the polybenzoxazole may also contain two or more different kinds of R ¹³¹ or R ¹³² , the A repeating unit represented by formula (X). In addition, in addition to the repeating unit of the formula (X), the polybenzoxazole may also contain other kinds of repeating structural units.

The polybenzoxazole can be obtained, for example, by oxazolating a polybenzoxazole precursor, which is a bisaminophenol derivative, It is obtained by reacting with a compound selected from the group consisting of a dicarboxylic acid containing R ¹³³ or a dicarboxylic acid dichloride and a dicarboxylic acid derivative thereof, and the like. Furthermore, in the case of dicarboxylic acid, in order to improve the reaction yield, etc., an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance can also be used. .

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. The bending resistance of the film after hardening can be improved by making a weight average molecular weight into 5,000 or more. In order to obtain a cured film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when two or more kinds of polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least one polybenzoxazole is in the above-mentioned range.

<<Method for producing polyimide precursor, etc.>> A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained by reacting with diamine after halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent. In the manufacturing method of a polyimide precursor etc., it is preferable to use an organic solvent when performing a reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be produced by heating and cyclization after synthesizing a polyimide precursor, or directly synthesizing polyimide.

＜＜＜Capping agent＞＞＞ In the production method of the polyimide precursor, etc., in order to further improve the storage stability, it is preferable to use an end capping agent such as an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, and a monoactive ester compound to cap the polyimide precursor. etc. end closure. As the blocking agent, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8 -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminosalicylic acid Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophene, 3-aminothiophene, 4-amine thiophene, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

＜＜＜Solid Precipitation＞＞＞ In the manufacture of a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, the solid precipitation can be performed by precipitating the polyimide precursor and the like in the reaction liquid into water and dissolving in a solvent such as tetrahydrofuran in which the polyimide precursor and the like can be dissolved. After that, the polyimide precursor and the like are dried to obtain a powdery polyimide precursor and the like.

The composition used in the present invention may contain only one of the polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole, or may contain two or more. In addition, two or more kinds of resins having the same kind and different structures may be included, such as two types of polyimide precursors. The content of the polyimide precursor and the like in the composition used in the present invention is preferably 10 to 99 mass % of the solid content, more preferably 50 to 98 mass %, still more preferably 70 to 70 mass % 96% by mass. Hereinafter, components that may be contained in the composition used in the present invention will be described. Of course, the present invention may also include components other than these, and these components are not required.

＜＜Polymerizable compound＞＞ As described above, in the present invention, it is preferable that the resin such as the polyimide precursor has a polymerizable group, or that the photosensitive resin composition contains a polymerizable compound. By setting it as such a structure, the cured film which is more excellent in heat resistance can be formed. The polymerizable compound is a compound having a polymerizable group, and a known compound that can undergo a crosslinking reaction by a radical, an acid, a base, or the like can be used. As a polymerizable group, the polymerizable group etc. which were described in the said polyimide precursor etc. can be illustrated. Only one type of polymerizable compound may be included, or two or more types may be included. The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and multimers of these.

In the present invention, the monomeric polymerizable compound (hereinafter, also referred to as a polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular weight compound, preferably a low molecular weight compound with a molecular weight of 2,000 or less, more preferably a low molecular weight compound with a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound with a molecular weight of 900 or less. In addition, the molecular weight of the polymerizable monomer is usually 100 or more. In addition, the oligomer-type polymerizable compound is typically a polymer with a relatively low molecular weight, preferably a polymer in which 10 to 100 polymerizable monomers are bonded. The weight average molecular weight of the oligomer-type polymerizable compound is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

The number of functional groups of the polymerizable compound in the present invention means the number of polymerizable groups in one molecule. From an analytical viewpoint, the polymerizable compound preferably contains at least one difunctional or more polymerizable compound containing two or more polymerizable groups, and more preferably contains at least one trifunctional or more polymerizable compound. Moreover, it is preferable that the polymerizable compound in this invention contains at least 1 type of polymerizable compound more than trifunctional from the point which can form a three-dimensional crosslinked structure and can improve heat resistance. In addition, it may be a mixture of a difunctional or lower polymerizable compound and a trifunctional or higher polymerizable compound.

＜＜＜Compounds with ethylenically unsaturated bonds＞＞＞ As a group which has an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth)acryloyl group, and a (meth)allyl group are preferable, and a (meth)acryloyl group is more preferable.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, The amides and the polymers thereof are preferably esters of unsaturated carboxylic acids and polyol compounds, amides of unsaturated carboxylic acids and polyamine compounds, and polymers thereof. In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, and addition reactants with monofunctional or polyfunctional isocyanates or epoxides can also be suitably used, or Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol, and further, having Substitution reaction products of unsaturated carboxylic acid esters or amides with a releasable substituent such as a halogen group or a tosyloxy group, and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, and the like may be used instead of the unsaturated carboxylic acid.

As a specific example of the monomer of the ester of a polyhydric alcohol compound and an unsaturated carboxylic acid, as an acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diacrylate are mentioned. , tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(acrylooxypropyl) ether, trimethylolpropane triacrylate Methylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate Esters, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(acryloyloxyethyl) Isocyanurate, isocyanuric ethylene oxide modified triacrylate, polyester acrylate oligomer, etc.

Examples of methacrylates include: tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate Esters, Trimethylolethane Trimethacrylate, Ethylene Glycol Dimethacrylate, 1,3-Butanediol Dimethacrylate, Hexylene Glycol Dimethacrylate, Pentaerythritol Dimethacrylate ester, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloyloxyethoxy)phenyl]dimethylmethane Wait.

As the itaconate ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate can be mentioned. , tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, etc.

Examples of the crotonate include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetra-dicrotonate, and the like.

As isocrotonate, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. are mentioned.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitan tetramaleate Diester, etc.

As examples of other esters, for example, aliphatic alcohols described in Japanese Patent Laid-Open No. 46-27926, Japanese Patent Laid-Open No. 51-47334, and Japanese Patent Laid-Open No. 57-196231 can also be suitably used. Esters, or those with aromatic skeletons described in Japanese Patent Laid-Open No. 59-5240, Japanese Patent Laid-Open No. 59-5241, and Japanese Patent Laid-Open No. Hei 2-226149, Japanese Patent Laid-Open No. 2-226149 Those containing an amine group described in Gazette 1-165613, and the like.

In addition, as a specific example of the monomer of polyamine compound and amide of unsaturated carboxylic acid, there are methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamide, xylylene bis-methacrylamide and the like.

As an example of another preferable amide-type monomer, what has a cyclohexylene structure as described in Unexamined-Japanese-Patent No. 54-21726 is mentioned.

In addition, a urethane-based addition polymerizable monomer produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, the description in Japanese Patent Laid-Open No. 48-41708 can be mentioned, for example. Ethylene containing two or more polymerizable vinyl groups in one molecule obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula to a polyisocyanate compound having two or more isocyanate groups in one molecule carbamate compounds, etc. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (wherein, R ⁴ and R ⁵ represent H or CH ₃ ) In addition, for example, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Hei 2- Acrylic urethanes described in Japanese Patent Publication No. 32293, Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, and Japanese Patent Publication No. 62 The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 39417 and Japanese Patent Publication No. Sho 62-39418 are also suitable.

In addition, in the present invention, as the compound having an ethylenically unsaturated bond, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be suitably used.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. ; Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloyloxypropyl) (meth)acrylic acid after adding ethylene oxide or propylene oxide to polyfunctional alcohol Those obtained by esterification, such as (meth)acrylate urethanes described in Japanese Patent Laid-Open No. 48-41708, Japanese Patent Laid-Open No. 50-6034, and Japanese Patent Laid-Open No. 51-37193 Types, polyester acrylates described in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191, and Japanese Patent Laid-Open No. 52-30490, as epoxy resins and (methyl) ) Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth)acrylate etc. obtained by making a polyfunctional carboxylic acid react with a compound which has a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth)acrylate, can also be mentioned. In addition, as other preferred compounds having an ethylenically unsaturated bond, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216 can also be used. A compound having a perylene ring and having two or more ethylenically unsaturated bond-containing groups, a cardo resin. Furthermore, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, or Japanese Patent Publication No. 1-40336 can also be cited. Vinylphosphonic acid-based compounds and the like described in Japanese Patent Laid-Open No. 2-25493. Moreover, in some cases, the structure containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-22048 is used suitably. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Japan Adhesion Association" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, compounds having an ethylenically unsaturated bond represented by the following formulae (MO-1) to (MO-5) can also be suitably used. In addition, in the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical 29]

[Chemical 30]

In the above formula, n is an integer of 0-14, and m is an integer of 0-8. A plurality of R and T in one molecule may be the same or different. In each of the polymerizable compounds represented by the above formulae (MO-1) to (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ , or -OC A group represented by (=O)C(CH ₃ )=CH ₂ . In the present invention, Japanese Patent Laid-Open No. 2007-269779 can also be suitably used as a specific example of the compound having an ethylenically unsaturated bond represented by the above formulae (MO-1) to (MO-5). Compounds described in paragraphs 0248 to 0251 of the gazette.

In addition, the following compounds described in Japanese Patent Laid-Open No. 10-62986 as formulas (1) and (2) together with specific examples thereof can also be used as polymerizable compounds, which are added to polyfunctional alcohols. A compound obtained by (meth)acrylic esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraph Nos. 0104 to 0131 of JP 2015-187211 A can also be used, and these contents are incorporated into the present specification. In particular, the compounds described in paragraphs 0128 to 0130 of JP 2015-187211 A can be exemplified as preferred embodiments.

As the compound having an ethylenically unsaturated bond, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available) The product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (the commercial product is KAYARAD) D-310; Nippon Kayaku Co., Ltd. Pharmaceutical Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd.), and the (meth)acryloyl group of these A compound having a structure bonded via ethylene glycol residues and propylene glycol residues. Oligomeric forms of these can also be used. Moreover, the pentaerythritol derivative and/or dipentaerythritol derivative of the said formula (MO-1) and formula (MO-2) can also be mentioned as a preferable example.

Commercially available products of the polymerizable compound include, for example, SR-494 which is a tetrafunctional acrylate having four ethoxy-extended chains, and SR-494 which is a difunctional methacrylate having four ethoxy-extended chains. -209 (the above are manufactured by Sartomer Japan Co., Ltd.), as DPCA-60 as a hexafunctional acrylate having 6 pentoxy-extended chains, as 3-isobutoxy-extended chains as DPCA-60 Functional acrylate TPA-330 (the above are manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers UAS-10 and UAB-140 (the above are manufactured by Sanyo Kokusaku Pulp Co., Ltd.) , NK Ester (NK Ester) M-40G, NK Ester (NK Ester) 4G, NK Ester (NK Ester) M-9300, NK Ester (NK Ester) A-9300, UA-7200 (the above are New Nakamura Chemical Industry ( Cos ), Blemmer PME400 (manufactured by NOF Corporation), etc.

As a compound having an ethylenically unsaturated bond, for example, Japanese Patent Laid-Open No. 48-41708, Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Laid-Open No. 2-16765 Acrylic urethanes described in the gazettes, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Urethane compounds having an ethylene oxide-based skeleton described in Gazette No. 1 are also suitable. Furthermore, as the polymerizable compound, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 1-105238 having an amino group in the molecule can also be used. Structure or thioether-based addition polymerizable monomers.

The compound having an ethylenically unsaturated bond may also be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably has an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol in the ester. As a commercial item, M-510, M-520 etc. which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. are mentioned, for example. The polyfunctional monomer which has an acid group may be used individually by 1 type, and may be used in mixture of 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed. The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH/g to 40 mgKOH/g, and particularly preferably 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is in the above range, the production or handling properties are excellent, and furthermore, the developability is excellent. In addition, the polymerizability is good.

The polymerizable compound having such a caprolactone structure is marketed by Nippon Kayaku Co., Ltd. as, for example, the KAYARAD DPCA series, and examples thereof include DPCA-20 (the above-mentioned formula (C) to formula (E) ), m=1, the number of groups represented by the formula (D)=2, and R ¹ is a compound in which both are hydrogen atoms), DPCA-30 (in the above formulas (C) to (E), m= 1. The number of groups represented by the formula (D)=3, and R ¹ is a compound in which both are hydrogen atoms), DPCA-60 (in the above formulas (C) to (E), m=1, and from the formula ( D) The number of groups represented by = 6, and R ¹ is a compound of hydrogen atoms), DPCA-120 (in the above formulas (C) to (E), m=2, represented by formula (D) The number of bases = 6, and R ¹ is a compound of hydrogen atoms) and so on. In the present invention, the compound having a caprolactone structure and an ethylenically unsaturated bond may be used alone or in combination of two or more.

In the composition, from the viewpoint of good polymerizability and heat resistance, the content of the compound having an ethylenically unsaturated bond is preferably 1% by mass to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 30 mass % or less. The compound which has an ethylenically unsaturated bond may be used individually by 1 type, and may be used in mixture of 2 or more types. In addition, the mass ratio of the polyimide precursor and the like to the compound having an ethylenically unsaturated bond (polyimide precursor and the like/polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/ 5～30/70, the best is 90/10～50/50. If the mass ratio of the polyimide precursor etc. and the compound which has an ethylenically unsaturated bond is the said range, the cured film which is more excellent in polymerizability and heat resistance can be formed.

<<<Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl>>> As a compound which has a hydroxymethyl group, an alkoxymethyl group, or an alkoxymethyl group, the compound represented by following formula (AM1) is preferable.

（式中，t表示1～20的整數，R⁴ 表示碳數1～200的t價的有機基，R⁵ 表示由下述式（AM2）或下述式（AM3）所表示的基）(AM1) [Chemical 31]

(in the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3))

（式中，R⁶ 表示羥基或碳數1～10的有機基）Formula (AM2) Formula (AM3) [Chemical 32]

(In the formula, R ⁶ represents a hydroxyl group or an organic group with 1 to 10 carbon atoms)

The compound represented by the formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyimide precursor or the like. More preferably, it is 10 mass parts or more and 35 mass parts or less. In addition, it is also preferable to contain 10 mass % or more and 90 mass % or less of the compound represented by the following formula (AM4) in all the polymerizable compounds, and 10 mass % or more, 90 mass % or less of the compound represented by the following formula (AM5).

（式中，R⁴ 表示碳數1～200的二價的有機基，R⁵ 表示由下述式（AM2）或下述式（AM3）所表示的基）(AM4) [Chemical 33]

(In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3))

（式中，u表示3～8的整數，R⁴ 表示碳數1～200的u價的有機基，R⁵ 表示由下述式（AM2）或下述式（AM3）所表示的基）(AM5) [Chemical 34]

(in the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3))

（式中，R⁶ 表示羥基或碳數1～10的有機基）Formula (AM2) Formula (AM3) [Chemical 35]

(In the formula, R ⁶ represents a hydroxyl group or an organic group with 1 to 10 carbon atoms)

By setting it as the said range, when a composition is hardened on the board|substrate which has unevenness|corrugation, it becomes less that cracks generate|occur|produce. It is excellent in pattern workability, and can have high heat resistance such that the 5% mass reduction temperature is 350°C or higher, more preferably 380°C or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML- PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are Trade name, Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (the above are trade names, Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-th Tributylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, etc.

In addition, specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML -TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), Nika NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

＜＜＜Epoxy compound (compound having epoxy group)＞＞＞ The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy base undergoes a cross-linking reaction at 200° C. or lower, and does not undergo a dehydration reaction caused by cross-linking, so film shrinkage hardly occurs. Therefore, it is effective to contain an epoxy compound for low-temperature hardening and warpage reduction of the composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus can be further reduced, and the warpage can be further reduced. Moreover, since flexibility is high, the cured film which is excellent also in elongation etc. can be obtained. 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 resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; Alkanediol-type epoxy resins; epoxy-containing silicones such as polymethyl(glycidoxypropyl)siloxane, etc., are not limited to these examples. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) ) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4880 (Epiclon) (registered trademark) EXA-4850-150, Epiclon (Epiclon) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA -4822 (trade name above, manufactured by DIC), Physicochemical resin (registered trademark) BEO-60E (trade name, manufactured by Nippon Chemical Corporation), EP-4003S, EP-4000S (above It is a trade name, manufactured by Adico (stock), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred in terms of low warpage and excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and physicochemical resin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups. .

The compounding amount of the epoxy compound is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and still more preferably 10 parts by mass to 40 parts by mass relative to 100 parts by mass of the polyimide precursor, etc. parts by mass. When the compounding amount is 5 parts by mass or more, the warpage of the cured film can be further suppressed, and when it is 50 parts by mass or less, pattern burying by reflow at the time of curing can be further suppressed.

<<<Oxetane compound (compound having an oxetanyl group) >>> Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, Yaron oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone or in combination of two more than one species.

The compounding amount of the oxetane compound is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and still more preferably 10 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like parts to 40 parts by mass.

＜＜＜Benzoxazine compounds (compounds having a benzoxazole group)＞＞＞ The benzoxazine compound undergoes a cross-linking reaction caused by a ring-opening addition reaction, so there is no degassing caused by curing, and further shrinkage caused by heat is small, so the generation of warpage can be suppressed, so it is relatively good.

Preferable examples of the benzoxazine compound include B-a-type benzoxazine, B-m-type benzoxazine (the above are trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), and polyhydroxystyrene resins. Benzoxazine adduct, phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The compounding amount of the benzoxazine compound is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and still more preferably 10 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like ~40 parts by mass.

＜＜Photopolymerization initiator＞＞ The composition used in the present invention may contain a photopolymerization initiator. In particular, since the composition contains a photopolymerization initiator, after the composition is applied to a semiconductor wafer or the like to form a composition layer, light is irradiated, whereby hardening caused by radicals occurs, and the light-irradiated portion can be cured. Solubility decreased. Therefore, for example, by exposing the composition layer through a photomask having a pattern for covering only the electrode portion, there is an advantage that regions with different solubility can be easily formed according to the pattern of the electrode.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction (crosslinking reaction) of the polymerizable compound by light, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferred. In addition, it may be an activator that generates active radicals by interacting with a photo-excited sensitizer in a certain way. The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm). The molar absorptivity of a compound can be measured by a known method. Specifically, for example, it is preferable to use an ethyl acetate solvent at a concentration of 0.01 g/L by means of an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). to measure.

As the photopolymerization initiator, known compounds can be used without limitation, and examples thereof include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), acyl group Acylphosphine compounds such as phosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxybenzene Ethyl ketone, azo compound, azide compound, metallocene compound, organic boron compound, iron aromatic complex, etc.

Examples of halogenated hydrocarbon derivatives having a triazine skeleton include compounds described in Wakabayashi et al., "Bulletin of the Chemical Society of Japan (Bull. Chem. Soc. Japan)", 42, 2924 (1969), British Patent No. 1388492 The compound described, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the specification of German Patent No. 3337024, the "J. Org. Chem." by F. C. Schaefer et al. ", 29, the compound described in 1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, the compound described in Japanese Patent Laid-Open No. 5-281728, the compound described in Japanese Patent Laid-Open No. 5-34920 Compounds described in Gazette No. 4,212,976, and the like.

Examples of compounds described in the specification of US Pat. No. 4,212,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-Trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-Tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -Tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-Trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-Oxadiazole, 2-Trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-Tribromomethyl-5-styryl- 1,3,4-oxadiazole, etc.) and so on.

In addition, examples of photopolymerization initiators other than those described above include compounds described in paragraph No. 0086 of Japanese Patent Laid-Open No. 2015-087611, Japanese Patent Laid-Open No. 53-133428, and Japanese Patent Laid-Open No. 2015-087611. Compounds and the like described in the specification of Japanese Patent Publication No. 57-1819, Japanese Patent Publication No. 57-6096, and US Pat. No. 3,615,455 are incorporated herein by reference.

As a ketone compound, the compound described in the paragraph No. 0087 of Unexamined-Japanese-Patent No. 2015-087611 can be illustrated, for example, and these content are incorporated in this specification. Among the commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As a photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. . As the hydroxyacetophenone-based starter, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: both are manufactured by BASF). As the aminoacetophenone-based starter, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF). As the aminoacetophenone-based initiator, compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength is matched to a long wavelength region such as 365 nm or 405 nm can also be used. As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. are mentioned. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF) and the like.

As a photopolymerization initiator, an oxime compound is mentioned more preferably. Exposure latitude can be improved more effectively by using oxime compounds. As specific examples of the oxime compound, compounds described in JP 2001-233842 A, compounds described in JP 2000-80068 A, and JP 2006-342166 A can be used Compounds described. Preferable oxime compounds include, for example, the following compounds, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2- Butanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2- Propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzyl)oxime, 1,3-diphenylpropanetri Keto-2-(O-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxyglycerol-2-(O-benzyl) oxime, etc. [Chemical 36]

Examples of the oxime compound include "J.C.S. Perkin II" (1979) pp.1653-1660, "J.C.S. Perkin II" (1979) Year) pp.156-162, "Journal of Photopolymer Science and Technology" (1995) pp.202-232, and Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open Compounds and the like described in respective publications of Gazette No. 2000-80068, JP 2004-534797 A, and JP 2006-342166 A. Commercially available products can also be appropriately used: IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), N-1919 (ADEKA) (stock) )manufacture). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), ADEKA arc Luz NCI-831 and ADEKA arc Luz NCI-930 can also be used (manufactured by Adiko Co., Ltd.). Alternatively, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can also be used.

作為最佳的肟化合物，可列舉：日本專利特開2007-269779號公報中所示的具有特定取代基的肟化合物、或日本專利特開2009-191061號公報中所示的具有硫代芳基的肟化合物等。In addition, compounds described in JP 2009-519904 A in which an oxime is linked to the N-position of carbazole, and a compound described in the specification of US Pat. No. 7,626,957 in which a heterosubstituent is introduced into the benzophenone moiety can also be used. The compounds described in Japanese Patent Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, the ketoxime compounds described in International Publication No. WO2009-131189, The compound described in US Pat. No. 7,556,910, which contains a triazine skeleton and an oxime skeleton in the same molecule, has a maximum absorption at 405 nm, and has good sensitivity to a g-ray light source. Compounds described, etc. Moreover, the cyclic oxime compound described in Unexamined-Japanese-Patent No. 2007-231000 and Unexamined-Japanese-Patent No. 2007-322744 can also be used suitably. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds described in Japanese Patent Laid-Open No. 2010-32985 and Japanese Patent Laid-Open No. 2010-185072 in carbazole dyes have high light absorption properties, It is preferable from the viewpoint of high sensitivity. Moreover, the compound described in Unexamined-Japanese-Patent No. 2009-242469 as a compound which has an unsaturated bond in a specific part of an oxime compound can also be used suitably. Furthermore, an oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Laid-Open No. 2010-262028, compounds 24 and 36 to Compound 40, compound (C-3) described in paragraph No. 0101 of Japanese Patent Laid-Open No. 2013-164471, and the like. Specific examples include the following compounds. [Chemical 37]

As the optimum oxime compound, the oxime compound having a specific substituent shown in Japanese Patent Laid-Open No. 2007-269779, or the thioaryl group shown in Japanese Patent Laid-Open No. 2009-191061 can be mentioned. oxime compounds, etc.

式（I） 式（I）中，R⁵⁰ 為碳數1～20的烷基；由一個以上的氧原子中斷的碳數2～20的烷基；碳數1～12的烷氧基；苯基；經碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基、由一個以上的氧原子中斷的碳數2～18的烷基及碳數1～4的烷基的至少一者取代的苯基；或聯苯基，R⁵¹ 為由式（II）所表示的基，或與R⁵⁰ 為相同的基，R⁵² ～R⁵⁴ 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化39]

式（II） 式中，R⁵⁵ ～R⁵⁷ 與所述式（I）的R⁵² ～R⁵⁴ 相同。From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably selected from a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acyl group Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene- Compounds in the group consisting of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds. The photopolymerization initiator is more preferably a trihalomethyltriazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, Benzophenone compounds, acetophenone compounds, and more preferably selected from trihalomethyltriazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one compound in the formed group is further preferably a metallocene compound or an oxime compound, particularly preferably an oxime compound. In addition, as the photopolymerization initiator, N,N'-tetraoxane such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) may also be used. yl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl- Aromatic ketones such as 1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, alkyl anthraquinones, etc., quinones condensed with aromatic rings, benzoin alkyl ethers, etc. Benzoin ether compounds, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. In addition, a compound represented by the following formula (I) can also be used. [Chemical 38]

Formula (I) In formula (I), R ⁵⁰ 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; benzene group; alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon interrupted by one or more oxygen atoms A phenyl group substituted by at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms; or a biphenyl group, where R ⁵¹ is a group represented by formula (II), or the same as R ⁵⁰ group, R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen. [Chemical 39]

Formula (II) In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ⁵⁴ in the above-mentioned formula (I).

In addition, as the photopolymerization initiator, the compounds described in Paragraph Nos. 0048 to 0055 of International Publication WO2015/125469 can also be used.

When the composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass relative to the total solid content of the composition, and further Preferably it is 0.1 mass % - 10 mass %. Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more kinds of photopolymerization initiators, it is preferable that the total of them is in the above-mentioned range.

<Migration inhibitor> It is preferable that the photosensitive resin composition used for the manufacturing method of this invention further contains a migration inhibitor. By including the migration inhibitor, the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition can be effectively suppressed. The migration inhibitor is not particularly limited, and examples include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetra azole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring) compounds, thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion-trapping agent that captures anions such as halogen ions can also be used. There is no restriction|limiting in particular as an ion scavenger, A conventionally well-known thing can be used. Particularly preferred is a hydrotalcite (hydrotalcite) represented by the following composition formula or a bismuth hydrous oxide represented by the following composition formula. Mg _1-X Al _X (OH) ₂ (CO ₃ ) _X/2 ·mH ₂ O (in the composition formula, 0<X≦0.5, and m is a positive number) BiO _x (OH) _y (NO ₃ ) _z ( In the above composition formula, 0.9≦x≦1.1, 0.6≦y≦0.8, 0.2≦z≦0.4) In addition, as a commercial product, the hydrotalcite can be obtained under the trade name of Kyowa Chemical Industry Co., Ltd.: DHT -4A. In addition, as a commercial item, the bismuth can be obtained under the trade name: IXE500 manufactured by Toagosei Co., Ltd. In addition, other ion scavengers may also be used as needed. For example, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like can be mentioned. These ion-trapping agents may be used alone or in combination of two or more.

As other migration inhibitors, the rust inhibitor described in paragraph No. 0094 of Japanese Patent Laid-Open No. 2013-15701, and the rust inhibitor described in paragraph No. 0073 to paragraph No. 0076 of Japanese Patent Laid-Open No. 2009-283711 can be used Compounds, the compounds described in Paragraph No. 0052 of Japanese Patent Laid-Open No. 2011-59656, the compounds described in Paragraph Nos. 0114, 0116 and 0118 of Japanese Patent Laid-Open No. 2012-194520, and the like.

When the composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01% by mass to 5.0% by mass, more preferably 0.05% by mass to 2.0% by mass, and still more preferably 0.1% by mass relative to the total solid content of the composition. % to 1.0% by mass. Only one kind of migration inhibitor may be sufficient as it, and two or more types may be sufficient as it. When there are two or more kinds of migration inhibitors, it is preferable that the sum of them is in the above-mentioned range.

＜＜Polymerization inhibitor＞＞ It is preferable that the photosensitive resin composition used for the manufacturing method of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallicol, p-tert-butylcatechol, 1,3,5 can be suitably used. -Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione , p-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl) -6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediene Aminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyl Quinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N -Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitors described in paragraph No. 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraph Nos. 0031 to 0046 of International Publication No. WO 2015/125469 can also be used. When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass relative to the total solid content of the composition. 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 sum of them is in the above-mentioned range.

<<Heat base generator>> The composition used for the manufacturing method of this invention may contain a heat base generator. The thermal alkali generator is not particularly limited in its kind, but preferably includes an acidic compound that generates a base when heated to 40° C. or higher, and an ammonium salt containing an anion having a pKa1 of 0 to 4 and an ammonium cation. at least one thermal base generator. Here, pKa1 means the logarithmic notation (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid. By preparing such a compound, the cyclization reaction of the polyimide precursor can be carried out at low temperature, and a composition with better stability can be formed. In addition, since the thermal base generator does not generate an alkali unless it is heated, even if it coexists with the polyimide precursor, cyclization of the polyimide precursor during storage can be suppressed, resulting in excellent storage stability.

The thermal alkali generator in the present invention contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40° C. or higher, and an ammonium salt (A2) having an anion and an ammonium cation having pKa1 of 0 to 4. The acidic compound (A1) and the ammonium salt (A2) generate bases when heated, so the bases generated from these compounds can promote the cyclization reaction of the polyimide precursor, and can be used in Cyclization of the polyimide precursor is performed at low temperature. In addition, even if these compounds are allowed to coexist with the polyimide precursor that is cyclized and hardened by an alkali, the cyclization of the polyimide precursor hardly proceeds unless heating is performed, so it is possible to A polyimide precursor composition with excellent stability was prepared. In addition, in this specification, the "acidic compound" refers to a compound in which 1 g of the compound is extracted into a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran=1/4) is added. , and stirred at room temperature for 1 hour. The solution was measured at 20°C using a pH meter, and the value was less than 7.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40°C or higher, more preferably 120°C to 200°C. The upper limit of the alkali generation temperature is more preferably 190°C or lower, more preferably 180°C or lower, and still more preferably 165°C or lower. The lower limit of the alkali generation temperature is more preferably 130°C or higher, and still more preferably 135°C or higher. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 40°C or higher, and further 120°C or higher, it is difficult to generate an alkali during storage, so that a polyimide precursor composition with excellent stability can be prepared. thing. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The alkali generation temperature can be measured, for example, using differential scanning calorimetry. The compound is heated to 250°C in a pressure-resistant capsule at 5°C/min, the peak temperature of the exothermic peak with the lowest temperature is read, and the peak temperature is determined as the alkali generation temperature. Determination.

In the present invention, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Due to the high basicity of tertiary amines, the cyclization temperature of the polyimide precursor can be further reduced. In addition, the boiling point of the alkali generated by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher. In addition, the molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of a molecular weight is a theoretical value calculated|required from a structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more compounds selected from ammonium salts and compounds represented by formula (101) or formula (102) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. Furthermore, the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120°C to 200°C), or may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120°C to 200°C). 120°C to 200°C is preferable), a compound other than an acidic compound which generates a base.

式中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，式R⁷ 表示烴基。R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 分別可鍵結而形成環。<<<Ammonium salt>>> In the present invention, the term ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, and may also have an anion outside the molecule of the ammonium cation, preferably an anion outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of an ammonium cation means the case where an ammonium cation and an anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation is also referred to as a counter anion. Equation (101) Equation (102) [Chemical 40]

In the formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and the formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may each be bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5). [Chemical 41]

In the above formula, R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ have the same meanings as those of formula (101) or formula (102). Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In the present invention, the ammonium salt preferably has an anion and an ammonium cation with pKa1 of 0-4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, still more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at low temperature, and the stability of the polyimide precursor composition can be improved. When pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of alkali without heating can be suppressed, and the stability of the polyimide precursor composition is good. When pKa1 is 0 or more, the generated base is difficult to neutralize, and the cyclization efficiency of the polyimide precursor is good. The type of the anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion, and is more preferably a carboxylate anion for the reason that the stability of the salt and thermal decomposability can coexist. . That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, a thermal alkali generator which can further improve the stability, curability, and developability of the polyimide precursor composition can be obtained. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the polyimide precursor composition can be further improved. In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, still more preferably 3.2 or less. According to this aspect, the stability of the polyimide precursor composition can be further improved. Here, the so-called pKa1 refers to the logarithm of the reciprocal of the first dissociation constant of an acid, and can refer to "Determination of Organic Structures by Physical Methods" (authors: Brown, H. C., McDaniel ( McDaniel, D. H., Hafliger, O., Nachod, F. C.; Editors: Braude, E. A., Nachod, F. C.; American Academic Press ( Academic Press), New York, 1955), or "Data for Biochemical Research" (authors: Dawson, R. M. C. et al; Oxford, Clarendon Press, 1959) the value recorded in . For compounds not described in these documents, the values calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs) were used.

式（X1）中，EWG表示拉電子基。In the present invention, the carboxylate anion is preferably represented by the following formula (X1). [Chemical 42]

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

In the present invention, the term "electron-withdrawing group" refers to a group having a positive value of Hammett's substituent constant σm. Here, σm is described in detail in Yufu Tono's general theory, "The Society of Organic Synthetic Chemistry", Vol. 23, No. 8 (1965), pp. 631-642. In addition, the electron withdrawing group in the present invention is not limited to the substituents described in the literature. Examples of substituents having a positive value for σm include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group ( σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. . In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。In the present invention, EWG preferably represents a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical 43]

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

式（X）中，L¹⁰ 表示單鍵，或選自伸烷基、伸烯基、芳香族基、-NR^X -及該些的組合中的二價的連結基，R^X 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylate anion is also preferably represented by the following formula (X). [Chemical 44]

In formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NR ^X - and a combination of these, and R ^X represents a hydrogen atom, Alkyl, alkenyl or aryl.

[化46]

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion. The thermal alkali generator which can be preferably used in the present invention is exemplified below. Of course, the thermal alkali generator that can be used in the present invention is not limited to these examples. [Chemical 45]

[Chemical 46]

（A-22）[Chemical 47]

(A-22)

When a hot alkali generator is used, the content of the hot alkali generator in the composition is preferably 0.1% by mass to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5 mass % or more, still more preferably 1 mass % or more. The upper limit is more preferably 30 mass % or less, still more preferably 20 mass % or less. One type or two or more types of thermal alkali generators can be used. When two or more types are used, it is preferable that the total amount is within the above-mentioned range.

＜＜Photobase generator＞＞ The photosensitive resin composition used for the manufacturing method of this invention may contain a photobase generator. The so-called photobase generators are those that generate alkalis by exposure, as long as they do not show activity under normal conditions of normal temperature and pressure, but generate alkalis (alkalis) when exposed to light, that is, irradiation with electromagnetic waves and heating as external stimuli. Substances) are not particularly limited. Since the alkali generated by exposure acts as a catalyst when the polyimide precursor is hardened by heating, it can be suitably used in the negative type.

The content of the photobase generator is not particularly limited as long as a desired pattern can be formed, and a normal content can be used. With respect to 100 parts by mass of the resin, the photobase generator is preferably in the range of 0.01 parts by mass to 30 parts by mass, more preferably in the range of 0.05 parts by mass to 25 parts by mass, and still more preferably in the range of 0.1 parts by mass to 20 parts by mass within the range of parts by mass.

In this invention, a well-known thing can be used as a photobase generator. For example, M. Shirai and M. Tsunooka, "Progress in Polymer Science, Prog. Polym. Sci.", 21, 1 (1996) Masahiro Kakuoka, "Polymer Processing", 46, 2 (1997); C. Kutal, "Coordination Chemistry Reviews, Coord. Chem. Rev.", 211, 353 (2001); Y. Y. Kaneko, A. Sarker, and D. Neckers, "Chemistry of Materials (Chem. Mater.)", 11, 170 (1999); H. . Tachi, M. Shirai, and M. Tsunooka, "Journal of Photopolymer Science and Technology, J. Photopolym. Sci. Technol .)”, 13, 153 (2000); M. Winkle, and. Graziano, “J. Photopolym. Sci. Technol.”, 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, "J. Photopolym. Sci . Technol.)", 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, "J. Photopolym . Sci. Technol.)", 19, 81 (2006), transition metal compound complexes, or those having structures such as ammonium salts, or those that are latentized by forming a salt with an amidine moiety and a carboxylic acid Generally, an ionic compound neutralized by forming a salt with an alkali component, or a urethane derivative, an oxime ester derivative, an acyl compound, etc., is subjected to a latent reaction by the alkali component through a urethane bond or an oxime bond. cationic non-ionic compounds. In the present invention, examples of the photobase generator include urethane derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, amide cinnamate derivatives, and oxime derivatives. as a better example.

Although it does not specifically limit as a basic substance which generate|occur|produces from a photobase generator, The compound which has an amine group, especially polyamines, such as a monoamine and a diamine, or an amidine, etc. are mentioned. The generated basic substance is preferably a compound having an amine group with higher basicity. The reason for this is that it has a strong catalytic effect with respect to the dehydration condensation reaction in the imidization of the polyimide precursor, and can exhibit a dehydration condensation reaction at a lower temperature when added in a smaller amount. catalyst effect in . That is, since the catalytic effect of the generated alkaline substance is large, the apparent sensitivity of the negative photosensitive resin composition is improved. From the viewpoint of the catalyst effect, amidines and aliphatic amines are preferred.

The photobase generator is preferably a photobase generator that does not contain a salt in its structure, and it is preferable that the photobase generator does not have a charge on the nitrogen atom of the generated base moiety. As a photobase generator, it is preferable that the generated base is latentized using a covalent bond, and the mechanism for generating the base is preferably that the covalent bond between the nitrogen atom of the generated base part and the adjacent atom is cut off. produce alkali. If it is a photobase generator which does not contain a salt in a structure, since a photobase generator can be neutralized, solvent solubility becomes more favorable, and a pot life (pot life) improves. For this reason, the amine produced from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

In addition, for the reasons described above, as the photobase generator, it is preferable to use a covalent bond for the generated base as described above, and it is more preferable to use an amide bond or an amine for the generated base. Formate bond and oxime bond for latentization. As the photobase generator in the present invention, for example, a photobase generator having a cinnamate structure as disclosed in Japanese Patent Laid-Open No. 2009-80452 and International Publication No. WO2009/123122, such as Photobase generators having a urethane structure as disclosed in Japanese Patent Laid-Open No. 2006-189591 and Japanese Patent Laid-Open No. 2008-247747, such as Japanese Patent Laid-Open No. 2007-249013 and Japanese Patent Laid-Open No. 2007-249013 Photobase generators having an oxime structure and a carbamoyl oxime structure as disclosed in Kokai Publication No. 2008-003581, etc., are not limited to these, and structures of known photobase generators can also be used. .

In addition, examples of the photobase generator include the compounds described in paragraphs 0185 to 0188, paragraphs 0199 to 0200, and paragraphs 0202 of Japanese Patent Laid-Open No. 2012-93746. Compounds described in paragraphs 0022 to 0069 of Japanese Patent Laid-Open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Laid-Open No. 2013-204019, and International Publication WO2010/064631 The compounds described in paragraph No. 0052 of Gazette No. 1 are exemplified.

As a commercially available photobase generator, WPBG-266, WPBG-300, WPBG-345, WPBG-140, WPBG-165, WPBG-027, WPBG-018, WPBG-015, WPBG-041, WPBG can also be used -172, WPBG-174, WPBG-166, WPBG-158, WPBG-025, WPBG-168, WPBG-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries Ltd.).

＜＜Thermal acid generator＞＞ The composition used in the production method of the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating, and promotes the cyclization of polyimide precursors, etc., and further improves the mechanical properties of the cured film. In addition, it also has the effect of promoting the crosslinking reaction of the following compounds. At least one selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an oxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 250°C or lower. In addition, if selecting the final heating ( Curing: when acid is generated at about 100°C to 400°C), a decrease in sensitivity at the time of image development can be suppressed, so it is preferable.

The acid generated by the autothermal acid generator is preferably a strong acid, such as arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid; alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, etc. Halogenated alkyl sulfonic acids such as methanesulfonic acid, etc. As an example of such a thermal acid generator, the thing described in the paragraph number 0055 of Unexamined-Japanese-Patent No. 2013-072935 is mentioned.

Among them, from the viewpoint of reducing the residue in the cured film and not reducing the physical properties of the cured film, it is more preferable to be a thermal acid which generates a C1-4 alkylsulfonic acid or a C1-4 halogenated alkylsulfonic acid Generating agents, more preferably (4-hydroxyphenyl) dimethyl perionium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethyl perilinium methanesulfonate, and benzyl methanesulfonate (4-Hydroxyphenyl)methyl perionium, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl perionate, (4-hydroxyphenyl)methyl methanesulfonate (( 2-Methylphenyl)methyl)perylium, (4-hydroxyphenyl)dimethylperylium trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)trifluoromethanesulfonate Dimethyl strontium, benzyl (4-hydroxyphenyl) methyl sulfamate trifluoromethanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methyl sulfanate trifluoromethanesulfonate, (4-Hydroxyphenyl)methyl((2-methylphenyl)methyl)perylene trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene -2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methanesulfonamido)-4-hydroxyphenyl)hexafluoropropane.

Moreover, the compound described in the paragraph No. 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the polyimide precursor and the like. By containing 0.01 mass part or more, since the cyclization of a crosslinking reaction, a polyimide precursor, etc. is accelerated, the mechanical property and chemical resistance of a cured film can be improved further. Moreover, from a viewpoint of the electrical insulating property of a cured film, 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are still more preferable. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above-mentioned range.

＜＜Thermal polymerization initiator＞＞ The composition used in the present invention may also contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor or the like is advanced. In addition, when the polyimide precursor or the like contains an ethylenically unsaturated bond, the cyclization of the polyimide precursor and the like can also be carried out together with the polymerization reaction of the polyimide precursor, etc., so that higher of heat resistance. Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, cyclones Metal compounds, active ester compounds, compounds having a carbon-halogen bond, azo compounds, and the like. Among them, peroxides or azo compounds are more preferred, and peroxides are particularly preferred. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90°C to 130°C, more preferably 100°C to 120°C. Specifically, the compounds described in Paragraph Nos. 0074 to 0118 of JP-A No. 2008-63554 can be mentioned. Among the commercially available products, Perbutyl Z and Percumyl D (manufactured by NOF Corporation) can be suitably used.

When the composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass relative to the total solid content of the composition. The mass % is particularly preferably 0.1 to 20 mass %. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it becomes easy to form a cured film which is more excellent in heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When two or more types of thermal radical polymerization initiators are used, it is preferable that the total of them is in the above-mentioned range.

相對於聚醯亞胺前驅物等100質量份，金屬接著性改良劑的含量較佳為0.1質量份～30質量份，更佳為0.5質量份～15質量份的範圍。藉由設為0.1質量份以上，熱硬化後的膜與金屬的接著性變得良好，藉由設為30質量份以下，硬化後的膜的耐熱性、機械特性變得良好。 金屬接著性改良劑可僅為一種，亦可為兩種以上。當使用兩種以上時，較佳為其合計為所述範圍。<<Metal Adhesion Improver>> It is preferable that the composition used in the production method of the present invention contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of the metal adhesion improver include those described in paragraphs 0046 to 0049 of JP 2014-186186 A, or paragraphs 0032 to 0043 of JP 2013-072935 A thioether compounds. In addition, the following compound (N-[3-(triethoxysilyl)propyl]maleic acid monoamide) can also be exemplified as the metal adhesion improving agent. [Chemical 48]

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass, relative to 100 parts by mass of the polyimide precursor and the like. By setting it as 0.1 mass part or more, the adhesiveness of the film and metal after thermosetting becomes favorable, and by setting it as 30 mass parts or less, the heat resistance and mechanical properties of the cured film become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more kinds are used, it is preferable that they add up to the said range.

＜＜Silane coupling agent＞＞ It is preferable that the composition used for the manufacturing method of this invention contains a silane coupling agent from the point of improving the adhesiveness with a board|substrate. Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, and the compounds described in paragraphs 0063 to 0071 of WO2011/080992A1. The compounds described, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Laid-Open No. 2014-41264, The compound described in paragraph 0055 of International Publication WO2014/097594. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. The content of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass, relative to 100 parts by mass of the polyimide precursor and the like. When it is 0.1 parts by mass or more, more sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above-mentioned range.

＜＜Sensitizing Pigment＞＞ The composition used in the production method of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in the electronically excited state is brought into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and functions such as electron transfer, energy transfer, and heat generation are generated. Thereby, the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator are chemically changed and decomposed to generate a radical, an acid, or a base.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (such as phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (such as fluorescein, eosin, luciferin, Danmin B, Rose Bengal), thioxanthones (such as 2,4-diethylthioxanthone), cyanines (such as thiacarbocyanine, oxacarbocyanine), merocyanine (e.g. merocyanine, carbocyanine), thiazides (e.g. thiazide, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), anthracene Quinones (such as anthraquinone), squaraines (such as squaraine), coumarins (such as 7-diethylamino-4-methylcoumarin, 3, 3'-Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamino Coumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-di ethylaminocoumarin), N-phenyldiethanolamine, styrylbenzenes, distyrylbenzenes, carbazoles, etc.

Among them, in the present invention, from the viewpoint of initial efficiency, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, and triphenylene), thioxanthones, and distyrylbenzene are preferred. A compound and a styrylbenzene compound are combined, and it is more preferable to use the compound which has an anthracene skeleton. As a particularly preferable specific compound, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, etc. are mentioned.

When the composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and still more preferably 0.5% by mass relative to the total solid content of the composition. % to 10% by mass. One of the sensitizing dyes may be used alone, or two or more of them may be used in combination.

＜＜Chain transfer agent＞＞ The composition used in the production method of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the 3rd edition of the Polymer Dictionary (edited by The Society of Polymer Science, 2005) pp. 683 to 684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These chain transfer agents can generate free radicals by supplying hydrogen to low-activity radical species, or by deprotonation after being oxidized, thereby generating free radicals. In particular, thiol compounds such as 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles can be preferably used Wait).

When the composition contains a chain transfer agent, the preferable content of the chain transfer agent is preferably 0.01 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, relative to 100 parts by mass of the total solid content of the composition. , particularly preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more kinds of chain transfer agents, it is preferable that the sum of them is in the above-mentioned range.

＜＜Surfactant＞＞ In the composition used in the production method of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, by including a fluorine-based surfactant, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, so that the uniformity of the coating thickness and the liquid saving property can be further improved. When a coating liquid containing a fluorine-based surfactant is used to form a film, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the surface to be coated is improved, and the surface to be coated is improved. The coatability of the surface is improved. Therefore, even in the case of forming a thin film with a thickness of about several μm with a small amount of liquid, it is effective in that it is possible to more appropriately form a film with a uniform thickness with little variation in thickness.

所述化合物的重量平均分子量例如為14,000。The fluorine content of the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having the fluorine content within this range is effective from the viewpoint of uniformity of the thickness of the coating film or liquid saving, and also has good solvent solubility. Examples of fluorine-based surfactants include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac ) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (the above are manufactured by DIC), Fluorad FC430 , Fluorad FC431, Fluorad FC171 (the above are manufactured by Sumitomo 3M (stock)), Surflon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (the above are manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (the above are Uno Law (OMNOVA) company) and so on. As the fluorine-based surfactant, a block polymer can also be used, and specific examples thereof include compounds described in Japanese Patent Laid-Open No. 2011-89090. In addition, the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [Chemical 49]

The weight average molecular weight of the compound is, for example, 14,000.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L31, Pluronic manufactured by BASF Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tyrol Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, Japan) ) (shares)) etc. In addition, Pionin D-6112-W manufactured by Takemoto Oil Co., Ltd., and NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd. (Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 ( Kyoeisha Chemical (stock), W001 (Yu Shang (stock)), etc.

As an anionic surfactant, W004, W005, W017 (made by Yushang Co., Ltd.) etc. are mentioned specifically,.

Examples of silicone-based surfactants include "Toray Silicone DC3PA", "Toray Silicone SH7PA", and "Toray Silicone" manufactured by Toray Dow Corning Co., Ltd. (Toray Silicone) DC11PA", "Toray Silicone (Toray Silicone) SH21PA", "Toray Silicone (Toray Silicone) SH28PA", "Toray Silicone (Toray Silicone) SH29PA", "Toray Silicone (Toray Silicone) SH29PA" Silicone) SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF- 4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "BYK307", "BYK323" manufactured by BYK Chemie Japan (Co., Ltd.) , "BYK330", etc.

When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition. Only one type of surfactant may be used, or two or more types may be used. When two or more types of surfactants are used, it is preferable that the total of the surfactants is in the above-mentioned range.

＜＜Higher fatty acid derivatives, etc.＞＞ In the composition used in the production method of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or docosamide may be added, and it may be added to the composition. During the drying process after coating, it tends to exist on the surface of the composition. When the composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1% by mass to 10% by mass relative to the total solid content of the composition. Only one type of higher fatty acid derivatives and the like may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives and the like, it is preferable that the total be within the above-mentioned range.

＜＜Solvent＞＞ When the composition used in the production method of the present invention is formed into a layer by coating, it is preferable to prepare a solvent. As the solvent, any known solvent can be used without limitation as long as the composition can be formed into a layer. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl Butyl acid, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g. methyl alkoxyacetate, alkoxyacetic acid ethyl ester, butyl alkoxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3 - Alkoxypropionate alkyl esters (such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (such as methyl 3-methoxypropionate, 3-methoxypropionate) acid ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (such as methyl 2-alkoxypropionate, Ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2-methylpropionate Acid ethyl ester (such as 2-methoxy-2-methyl propionate methyl ester, 2-ethoxy-2-methyl propionate ethyl ester, etc.), pyruvate methyl ester, pyruvate ethyl ester, pyruvate propyl ester Esters, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl group can be suitably used Ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, Toluene, anisole, limonene, etc., and, as the sulfites, dimethyl sulfite can be suitably mentioned.

From the viewpoint of improvement of coating surface properties, etc., a form in which two or more kinds of solvents are mixed is also preferable. Among them, the following mixed solution is preferred, which contains methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol Two or more of acid esters, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone in combination.

When the composition contains a solvent, from the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid content concentration of the composition is 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass The mass % is particularly preferably 10 to 60 mass %. Only one solvent may be used, or two or more types may be used. When there are two or more kinds of solvents, it is preferable that the sum of them is in the above-mentioned range. In addition, from the viewpoint of film strength, with respect to the total mass of the composition, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide And the content of N,N-dimethylformamide is preferably less than 5 mass %, more preferably less than 1 mass %, further preferably less than 0.5 mass %, particularly preferably less than 0.1 mass %.

＜＜Other additives＞＞ Various additives such as inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, Anti-agglomeration agent, etc. When these additives are blended, it is preferable that the total blending amount thereof be 3 mass % or less of the solid content of the composition.

From the viewpoint of coating surface properties, the water content of the composition used in the production method of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, particularly preferably less than 0.6% by mass .

From the viewpoint of insulating properties, the metal content of the composition used in the production method of the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When a plurality of metals are included, it is preferable that the sum of these metals is in the above-mentioned range. In addition, as a method for reducing the metal impurities unintentionally contained in the composition, methods such as selecting a raw material with a small metal content as a raw material constituting the composition, filtering the raw material constituting the composition with a filter, and placing the The distillation is carried out under conditions that suppress contamination as much as possible by lining with polytetrafluoroethylene or the like.

From the viewpoint of wiring corrosion, the content of halogen atoms in the composition used in the production method of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, particularly preferably less than 200 mass ppm. ppm. Among them, those in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the total of chlorine atoms and bromine atoms, or chloride ions and bromide ions are in the above ranges, respectively.

Manufacturing method of semiconductor element In addition, the present invention discloses a method of manufacturing a semiconductor element including the method of manufacturing the laminate. Hereinafter, an embodiment of a semiconductor element using the laminate obtained by the method for producing the laminate of the present invention will be described. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounted element, and a semiconductor device 101 in which a plurality of semiconductor devices (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring board 120 . In addition, in this embodiment, the case where the number of laminated layers of the semiconductor device (semiconductor wafer) is 4 layers is mainly explained, but the number of laminated layers of the semiconductor device (semiconductor wafer) is not particularly limited. 8 floors, 16 floors, 32 floors, etc. In addition, it may be one layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a silicon substrate. The semiconductor device 101a in the uppermost stage does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor devices 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor device.

The semiconductor device 101 has a structure in which a semiconductor device 101 a without a through electrode and a semiconductor device 101 b to 101 d having a through electrode 102 b to 102 d are flip-chip connected. That is, the electrode pad of the semiconductor device 101a without the through electrode is connected to the adjacent connection pad on the semiconductor device 101a side of the semiconductor device 101b with the through electrode 102b by the metal bump 103a such as a solder bump. The connection pad on the other side of the semiconductor device 101b of the electrode 102b and the connection pad on the semiconductor device 101b side of the semiconductor device 101c having the through electrode 102c adjacent thereto are connected by metal bumps 103b such as solder bumps. Similarly, the connection pads on the other side of the semiconductor device 101c having the through electrodes 102c and the connection pads on the semiconductor device 101c side of the semiconductor device 101d having the through electrodes 102d adjacent thereto are made of metal bumps 103c such as solder bumps. to connect.

An underfill layer 110 is formed in the gap between each of the semiconductor devices 101 a to 101 d , and each of the semiconductor devices 101 a to 101 d is laminated via the underfill layer 110 .

The semiconductor device 101 is laminated on the wiring board 120 . As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, and a glass substrate as a base material is used. As the wiring board 120 to which the resin board is applied, a multilayer copper-clad laminate (multilayer printed wiring board) and the like are exemplified.

A surface electrode 120 a is provided on one surface of the wiring board 120 . The insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring board 120 and the semiconductor device 101 , and the wiring board 120 and the semiconductor device 101 are electrically connected via the rewiring layer 105 . The insulating layer 115 is the exposed photosensitive resin composition layer (resin layer) in the present invention. The insulating layer will be described in detail below. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor device 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Also, an underfill layer 110 a is formed between the insulating layer 115 and the semiconductor device 101 . In addition, an underfill layer 110 b is formed between the insulating layer 115 and the wiring board 120 .

2 shows an example of a layered product (rewiring layer) obtained by the production method of the present invention, 200 is a layered product obtained by the method of the present invention, 201 is a photosensitive resin composition layer (resin layer), and 203 is metal layer. In FIG. 2 , the metal layer 203 is a layer indicated by diagonal lines. The photosensitive resin composition layer 201 is formed into a desired pattern by negative development. The metal layer 203 is formed so as to cover a part of the surface of the pattern, and a photosensitive resin composition layer (resin layer) 201 is further laminated on the surface of the metal layer 203 . Furthermore, the photosensitive resin composition layer (resin layer) functions as an insulating film, the metal layer functions as a wiring layer, and is incorporated in the above-described semiconductor device as a rewiring layer. [Example]

Hereinafter, an Example is given and this invention is demonstrated more concretely. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are the quality standards.

<Synthesis Example 1> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and benzyl alcohol (A-1: Polyimide having no radical polymerizable group) Synthesis of precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (obtained by drying pyromellitic acid at 140° C. for 12 hours) and 14.22 g (131.58 mmol) of Benzyl alcohol was suspended in 50 mL of N-methylpyrrolidone and dried over molecular sieves. The suspension was heated at 100°C for 3 hours. A clear solution was obtained after several minutes of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10°C±4°C. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine in 100 mL of N-methylpyrrolidone over 20 minutes at 20°C to 23°C Added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding to 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected by filtration again. Next, the obtained polyimide precursor (A-1) was dried at 45° C. for 3 days under reduced pressure. (A-1) [Chemical 50]

<Synthesis Example 2> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate (A-2: having a radically polymerizable group) Synthesis of polyimide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (produced by drying pyromellitic acid at 140°C for 12 hours), 18.6 g (129 mmol) molar) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diglyme) were mixed and added to It stirred at the temperature of 60 degreeC for 18 hours, and produced the diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl ₂ , in the same manner as in Synthesis Example 1, it was converted into a polyimide precursor with 4,4'-oxydiphenylamine, and was used with The polyimide precursor (A-2) was obtained in the same manner as in Synthesis Example 1. (A-2) [Chemical 51]

<Synthesis example 3> [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-oxydiphenylamine and 2-hydroxyethyl methacrylate (A-3 : Synthesis of a polyimide precursor having a radically polymerizable group)] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (4,4 '-oxydiphthalic acid dried for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme was mixed and stirred at a temperature of 60° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl ₂ , in the same manner as in Synthesis Example 1, it was converted into a polyimide precursor with 4,4'-oxydiphenylamine, and was used with The polyimide precursor (A-3) was obtained in the same manner as in Synthesis Example 1. (A-3) [Chemical 52]

<Synthesis example 4> [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride and 4,4'-oxydiphenylamine (A-4: Polyimide precursor having a carboxyl group) 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic acid was dried at 140°C for 12 hours to obtain NMP) was dissolved in 180 mL of N-methyl-2-pyrrolidone (NMP), and 21.43 g (270.9 mmol) of pyridine was added, and the reaction solution was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine was dissolved in 100 mL of NMP by dropwise addition over 30 minutes. , and then the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated by adding to 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected by filtration again. Next, the obtained polyimide precursor (A-4) was dried at 45° C. for 3 days under reduced pressure. (A-4) [Chemical 53]

<Synthesis Example 5> [Polyimide precursor derived from pyromellitic dianhydride, m-tolidine and 2-hydroxyethyl methacrylate (A-5: having a radical polymerizable group) Synthesis of polyimide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (produced by drying pyromellitic acid at 140°C for 12 hours), 18.6 g (129 mmol) molar) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and heated at 60°C. The mixture was stirred at the temperature for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10°C±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, at 20°C to 23°C, a solution obtained by dissolving 12.46 g (58.7 mmol) of bim-toluidine in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture for 20 minutes. middle. Then, the reaction mixture was stirred at room temperature overnight. Next, the polyimide precursor was precipitated by adding to 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected by filtration again. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-5). (A-5) [Chemical 54]

<Synthesis example 6> [Synthesis of polymer (RA-1) for comparative example] 27.0 g (153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropylmethyl acrylamide, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, polymerization initiator (V-601, Wako Pure Chemical Industries, Ltd.) Manufacturing) 3.55 g (15.4 mmol), and 300 g of 3-methoxy-2-propanol were mixed. The mixture was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75°C under nitrogen atmosphere over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 75° C. for 2 hours under a nitrogen atmosphere. After the reaction was completed, the polymer was precipitated by adding to 5 liters of water and stirred at 5000 rpm for 15 minutes. The acrylic resin was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected by filtration again. Next, the obtained acrylic resin (RA-1) was dried at 45° C. for 3 days under reduced pressure. The numerical value in the following chemical formula (RA-1) is the mass ratio of the raw material monomers. (RA-1) [Chemical 55]

<Examples and Comparative Examples> The components described below were mixed to prepare a uniform solution, and a coating liquid of the photosensitive resin composition was prepared. <<Composition of photosensitive resin composition>> (A) Resin: parts by mass described in Table 1 (B) Polymerizable compound: parts by mass described in Table 1 (C) Photopolymerization initiator: parts by mass described in Table 1 (D) Polymerization inhibitor: parts by mass described in Table 1 γ-Butyrolactone: 60.00 parts by mass

[Table 1] (A) Resin (B) Polymerizable compound (C) Photopolymerization initiator (D) Polymerization inhibitor type added amount type added amount type added amount type added amount Photosensitive resin composition 1 A-1 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 2 A-2 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 3 A-3 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 4 A-4 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 5 A-5 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 6 A-6 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 7 A-3 32 B-2 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 8 A-3 32 B-1 6.88 C-2 1.04 D-1 0.08 Photosensitive resin composition 9 A-3 32 B-1 6.88 C-1 1.04 D-2 0.08 Photosensitive resin composition 10 RA-1 32 B-1 6.88 C-1 1.04 D-1 0.08 Photosensitive resin composition 11 RA-2 32 B-1 6.88 C-1 1.04 D-1 0.08

Abbreviations described in Table 1 are as follows. (A) Resin Resins synthesized in Synthesis Example 1 to Synthesis Example 5: A-6: Matrimid 5218 (manufactured by Huntsman Corporation, polyimide) Polymer (RA-2) for Comparative Example: Polymethyl methacrylate (Mw: 15,000, manufactured by Sigma-Aldrich Japan)

B-2：NK酯（NK ESTER）A-9300（新中村化學工業公司製造、三官能丙烯酸酯、下述結構） [化57]

(B) Polymerizable compound B-1: SR-209 (manufactured by Nippon Sadolan Co., Ltd., difunctional methacrylate, the following structure) [Chemical 56]

B-2: NK Ester (NK ESTER) A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional acrylate, the following structure) [Chemical 57]

(C) Photopolymerization initiator C-1: IRGACURE OXE-01 (manufactured by BASF) C-2: IRGACURE-784 (manufactured by BASF)

(D) Polymerization inhibitor D-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

Each photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness described in the table below on the silicon wafer. . Using a stepper (Nikon NSR 2005 i9C), at a wavelength of 365 nm, the photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² , and the photosensitive resin composition layer was exposed by cyclohexanone. The exposed photosensitive resin composition layer (resin layer) was developed for 60 seconds to form pores having a diameter of 10 μm. Then, the temperature was raised from room temperature at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and heating was performed for 3 hours after reaching 250° C. (maximum heating temperature). After cooling to room temperature, a metal layer (copper layer) having a thickness of 5 μm was formed on a part of the surface of the photosensitive resin composition layer (resin layer) by vapor deposition, thereby forming a laminate 1 . After irradiating the surfaces of the metal layer (copper layer) and the resin layer of the laminated body 1 with the plasma of the gas species described in the table below, the photosensitive resin composition was repeated using the same photosensitive resin composition as described above. Layer formation, exposure, development, and heating are performed to obtain the layered body 2 . A metal layer (copper layer) was formed on the surface of the layered body 2 by the vapor deposition method in the same manner as described above, and after irradiating the plasma of the gas species described in the table below again, the same photosensitivity as described above was used again. For the resin composition, the formation of the photosensitive resin composition layer, exposure, development, and heating were repeatedly performed to obtain the laminate 3 . Moreover, in Example 27 - Example 30, the said plasma process was changed, and the corona discharge process was performed, and the laminated body 2 was produced.

＜Evaluation＞ ＜＜Evaluation of Peeling Defect＞＞ (without heat treatment) For each of the laminates 2 and 3 obtained above, the part where the resin layer contacts the resin layer and the part where the metal layer contacts the resin layer are cut out so that the width in the vertical direction with respect to the resin layer is 5 mm. A part, the cross section was observed, and the presence or absence of peeling between the resin layer/resin layer and the metal layer/resin layer in one section was confirmed with an optical microscope. As long as no peeling occurs, it shows that it has excellent adhesiveness, and it becomes a preferable result. A: No peeling occurred B: One to two peelings occurred C: 3 to 5 peelings occurred D: 6 or more peelings occurred (with heat treatment) The layered body 2 and the layered body 3 obtained above were heated at 300° C. for 3 hours in nitrogen. Then, with respect to each layered product, the part where the resin layer contacts the resin layer and the part where the metal layer contacts the resin layer was cut out so that the width in the vertical direction with respect to the resin layer would be 5 mm, and the cross-section was analyzed. The presence or absence of peeling between the resin layer/resin layer and the metal layer/resin layer in one section was observed and confirmed with an optical microscope. As long as no peeling occurs, it shows that it has excellent adhesiveness, and it becomes a preferable result. A: No peeling occurred B: One to two peelings occurred C: 3 to 5 peelings occurred D: 6 or more peelings occurred

[Table 2] Photosensitive resin composition plasma treatment Laminate Peel defect (resin layer/resin layer) Peel defects (between metal layers/resin layers) type Film thickness gas species With or without irradiation no heating After heating at 300°C no heating After heating at 300°C Example 1 Photosensitive resin composition 1 16 μm oxygen Have 2 A B B B Example 2 Photosensitive resin composition 2 16 μm oxygen Have 2 A A A A Example 3 Photosensitive resin composition 3 16 μm oxygen Have 2 A A A A Example 4 Photosensitive resin composition 4 16 μm oxygen Have 2 B B A A Example 5 Photosensitive resin composition 5 16 μm oxygen Have 2 A B B B Example 6 Photosensitive resin composition 6 16 μm oxygen Have 2 B B A B Example 7 Photosensitive resin composition 7 16 μm oxygen Have 2 A A B B Example 8 Photosensitive resin composition 8 16 μm oxygen Have 2 A B A A Example 9 Photosensitive resin composition 9 16 μm oxygen Have 2 A A A A Comparative Example 1 Photosensitive resin composition 10 16 μm oxygen Have 2 C C D D Comparative Example 2 Photosensitive resin composition 11 16 μm oxygen Have 2 C D D D Comparative Example 3 Photosensitive resin composition 1 16 μm none none 2 B C D D Comparative Example 4 Photosensitive resin composition 2 16 μm none none 2 B C C D Comparative Example 5 Photosensitive resin composition 3 16 μm none none 2 B C C D Comparative Example 6 Photosensitive resin composition 4 16 μm none none 2 C C D D [table 3] Photosensitive resin composition plasma treatment Laminate Peel defect (resin layer/resin layer) Peel defects (between metal layers/resin layers) type Film thickness gas species With or without irradiation no heating After heating at 300°C no heating After heating at 300°C Example 10 Photosensitive resin composition 1 16 μm oxygen Have 3 B C B B Example 11 Photosensitive resin composition 2 16 μm oxygen Have 3 A A A A Example 12 Photosensitive resin composition 3 16 μm oxygen Have 3 A A A A Example 13 Photosensitive resin composition 4 16 μm oxygen Have 3 B C A A Example 14 Photosensitive resin composition 5 16 μm oxygen Have 3 B C B C Example 15 Photosensitive resin composition 6 16 μm oxygen Have 3 B C B B Example 16 Photosensitive resin composition 7 16 μm oxygen Have 3 A A B B Example 17 Photosensitive resin composition 8 16 μm oxygen Have 3 A B A A Example 18 Photosensitive resin composition 9 16 μm oxygen Have 3 A A A A Comparative Example 7 Photosensitive resin composition 10 16 μm oxygen Have 3 D D D D Comparative Example 8 Photosensitive resin composition 11 16 μm oxygen Have 3 D D D D Comparative Example 9 Photosensitive resin composition 1 16 μm none none 3 C C D D Comparative Example 10 Photosensitive resin composition 2 16 μm none none 3 C C D D Comparative Example 11 Photosensitive resin composition 3 16 μm none none 3 C C D D Comparative Example 12 Photosensitive resin composition 4 16 μm none none 3 C D D D [Table 4] Photosensitive resin composition plasma treatment Laminate Peel defect (resin layer/resin layer) Peel defects (between metal layers/resin layers) type Film thickness gas species With or without irradiation no heating After heating at 300°C no heating After heating at 300°C Example 19 Photosensitive resin composition 1 16 μm Argon Have 2 B C C C Example 20 Photosensitive resin composition 2 16 μm Argon Have 2 B B B B Example 21 Photosensitive resin composition 1 16 μm nitrogen Have 2 B B B B Example 22 Photosensitive resin composition 2 16 μm nitrogen Have 2 B B B B [table 5] Photosensitive resin composition plasma treatment Laminate Peel defect (resin layer/resin layer) Peel defects (between metal layers/resin layers) type Film thickness gas species With or without irradiation no heating After heating at 300°C no heating After heating at 300°C Example 23 Photosensitive resin composition 1 16 μm Argon Have 3 B C B C Example 24 Photosensitive resin composition 2 16 μm Argon Have 3 B B B B Example 25 Photosensitive resin composition 1 16 μm nitrogen Have 3 C C B C Example 26 Photosensitive resin composition 2 16 μm nitrogen Have 3 B B B B [Table 6] Photosensitive resin composition corona discharge treatment Laminate Peel defect (resin layer/resin layer) Peel defects (between metal layers/resin layers) type Film thickness energy With or without irradiation no heating After heating at 300°C no heating After heating at 300°C Example 27 Photosensitive resin composition 1 16 μm 2000 J/m ² Have 2 C C C C Example 28 Photosensitive resin composition 2 16 μm 2000 J/m ² Have 2 B C B C Example 29 Photosensitive resin composition 1 16 μm 4000 J/m ² Have 2 B C C C Example 30 Photosensitive resin composition 2 16 μm 4000 J/m ² Have 2 B B B C

As is clear from the results, the laminate obtained by the production method of the present invention is excellent in any of the adhesiveness between the resin layer and the resin layer and the adhesiveness between the metal layer and the resin layer. On the other hand, when a resin other than a polyimide precursor or the like was used as the resin (Comparative Example 1, Comparative Example 2, Comparative Example 7, and Comparative Example 8), the adhesion between the resin layer and the resin layer and the metal The adhesion between the layer and the resin layer is poor. In addition, when the surface activation treatment was not performed, both or one of the adhesion between the resin layer and the resin layer and the metal layer and the resin layer were poor (Comparative Examples 3 to 6, Comparative Examples 9 to 12) .

A layered body was formed and evaluated in the same manner except that the thicknesses of the resin layers of Example 2 and Example 9 were changed to 10 μm, 20 μm, and 30 μm, respectively. 9 equally good results.

In Example 18, the photosensitive resin composition 2 was used to form the resin layer of the second layer, and as a result, the same excellent effects as in Example 18 were obtained. In Example 18, except having changed the metal layer (copper thin film) to an aluminum thin film, it carried out similarly, and the result was the same favorable result as Example 18.

100: Semiconductor Components 101a to 101d: Semiconductor Devices 101: Laminate 102b～102d: through electrodes 103a～103e: Metal bumps 105: Rewiring layer 110, 110a, 110b: underfill layer 115: Insulation layer 120: Wiring substrate 120a: Surface Electrode 200: Laminate 201: Photosensitive resin composition layer (resin layer) 203: Metal Layer

FIG. 1 is a schematic diagram showing the configuration of an embodiment of a semiconductor element. FIG. 2 is a schematic diagram showing the configuration of an embodiment of a layered product obtained by the production method of the present invention.

200: Laminate

201: Photosensitive resin composition layer (resin layer)

203: Metal Layer

Claims (20)

A method for manufacturing a laminate, comprising: a photosensitive resin composition layer forming step, applying the photosensitive resin composition to a substrate to form a layer; an exposing step, exposing the photosensitive resin composition layer; developing treatment step of performing negative development treatment on the exposed photosensitive resin composition layer; metal layer forming step of forming a metal layer on a part of the surface of the photosensitive resin composition layer after the development treatment; and surface activation The treatment step includes subjecting at least a part of the metal layer and at least a part of the photosensitive resin composition layer to a surface activation treatment, and further includes performing the photosensitive resin composition layer forming step, the photosensitive resin composition layer forming step, the In the exposure step and the development treatment step, the photosensitive resin composition comprises a resin selected from the group consisting of polyimide precursors, polyimide precursors, polybenzoxazole precursors and polybenzoxazoles, and further It suffices that the resin contains at least one of a polymerizable group and the photosensitive resin composition contains a polymerizable compound. The method for producing a laminate according to claim 1, wherein the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are performed 3 to 7 times in the following order. The manufacturing method of the laminated body of Claim 1 or Claim 2 in which the said metal layer contains copper. The method for producing a laminate according to claim 1 or claim 2, wherein the resin is a polyimide precursor or a polybenzoxazole precursor. The method for producing a layered product according to claim 1 or claim 2, wherein the resin contains a partial structure represented by -Ar-L-Ar-; wherein Ar is independently an aromatic group, and L is an aromatic group containing A fluorine atom-substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, and a combination of two or more of the above. The method for producing a laminate according to claim 1 or claim 2, wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment. The manufacturing method of the laminated body of Claim 1 or Claim 2 whose said photosensitive resin composition contains a photopolymerization initiator. The manufacturing method of the laminated body of Claim 1 or Claim 2 whose content of the said resin is 50 mass % or more of the solid content in the said photosensitive resin composition. The manufacturing method of the laminated body of Claim 1 or Claim 2 in which the said photosensitive resin composition contains the polymerizable compound more than bifunctional. The method for producing a laminate according to claim 1 or claim 2, wherein the resin contains a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (4), the following The repeating unit represented by the formula (3) and at least one repeating unit in the group formed by the repeating unit represented by the following formula (X);

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 a hydrogen atom or Monovalent organic group;

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group;

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 (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. The method for producing a laminate according to claim 10, wherein the A ¹ and A ² are oxygen atoms. The manufacturing method of the laminated body of Claim 1 or Claim 2 in which the said resin contains a polymerizable group. The method for producing a laminate according to claim 12, wherein the polymerizable group is selected from the group consisting of a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group , at least one of the group consisting of oxetanyl, benzoxazoline and blocked isocyanate groups. The method for producing a laminate according to claim 1 or claim 2, wherein the surface activation treatment is plasma treatment. The method for producing a layered body according to claim 14, wherein the source gas in the plasma treatment is oxygen, hydrogen, argon, nitrogen, a mixed gas of nitrogen and hydrogen, or a mixed gas of argon and oxygen. The method for producing a layered product according to claim 1 or claim 2, wherein the development treatment is performed by performing the photosensitive resin composition layer forming step, the exposure step, and the development treatment step again. The subsequent photosensitive resin composition layer is a layer in contact with the metal layer subjected to the surface activation treatment and the photosensitive resin composition layer subjected to the surface activation treatment. The method for producing a laminate according to claim 1 or claim 2, wherein the photosensitive resin composition layer formation is performed 3 to 7 times in the following order step, the exposure step, the development treatment step, the metal layer formation step, and the surface activation treatment step. A method of manufacturing a semiconductor element including the method of manufacturing a laminate according to any one of Claims 1 to 17. A method for producing a rewiring layer, comprising: a step of forming a desired pattern including a photosensitive resin composition layer by negative development; a step of forming a metal layer obtained by the step of forming the pattern A metal layer is formed on a part of the surface of the pattern containing the photosensitive resin composition layer; in the surface activation treatment step, at least a part of the metal layer and at least a part of the pattern containing the photosensitive resin composition layer are performing surface activation treatment; and the steps of laminating a photosensitive resin composition layer on the surface of the metal layer, the photosensitive resin composition layer in the step of forming the pattern, and the photosensitive resin composition layer in the step of laminating The photosensitive resin composition layers are respectively a layer formed by a photosensitive resin composition comprising a resin selected from the group consisting of polyimide precursors, polyimide precursors, polybenzoxazole precursors and polybenzoxazoles, Furthermore, it satisfies at least one that the resin contains a polymerizable group and the photosensitive resin composition contains a polymerizable compound. The manufacturing method of the manufacturing method of the rewiring layer of claim 19, wherein the step of performing the lamination is to cover the surface of the metal layer and the The step of laminating a photosensitive resin composition layer on the surface of the pattern containing the photosensitive resin composition layer.

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