TW201826392A - Process for producing layered product and process for producing electronic device - Google Patents

Abstract

Provided are a process for producing a layered product having excellent adhesion and a process for producing an electronic device. The process for producing a layered product comprises: a photosensitive resin composition layer formation step; an exposure step; a development step; a heating step; and a metal layer formation step. A holding step in which after the surface temperature becomes a certain temperature, the surface is held in such state for 5 minutes or longer is conducted in at least one period selected from among between the photosensitive-resin composition layer formation step and the exposure step, between the exposure step and the development step, between the development step and the heating step, and between the heating step and the metal layer formation step.

Description

Manufacturing method of laminated body and manufacturing method of electronic component

The present invention relates to a method for manufacturing a laminated body and a method for manufacturing an electronic component.

Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulation properties, and are therefore used in insulating layers and the like of electronic components. In addition, polyfluorine and polybenzoxazole have low solubility in solvents. Therefore, they are also applied to precursors (polyfluorine imide and polybenzoxazole precursor) before the cyclization reaction. After the support body is heated, the polyimide precursor and the polybenzoxazole precursor are cyclized to form a cured film.

For example, Patent Documents 1 and 2 describe a case where a pattern cured film is produced using a photosensitive resin composition containing a polyfluorene imide precursor and a photopolymerization initiator. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-191749 [Patent Document 2] Japanese Patent Laid-Open No. 2014-201695

The present inventors studied a photosensitive resin composition containing a resin and a photopolymerization initiator selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. As a result, it was found that the film formed using the photosensitive resin composition containing these resins may not have sufficient adhesion to a support, a metal layer, or the like.

An object of the present invention is to provide a method for producing a laminated body having excellent adhesion and a method for producing an electronic component.

Based on the above problems, the inventors conducted research and found that there is a tendency to use a resin containing a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. After the film formed of the photosensitive resin composition of the photopolymerization initiator is applied to the support, it takes time to stabilize the properties of the film. In addition, it was found that by setting a predetermined storage process in any of the processes described later, a laminated body having excellent adhesion can be manufactured, and the above-mentioned problems are solved. The present invention provides the following. <1> A method for manufacturing a laminated body, comprising: a process for forming a photosensitive resin composition layer; and applying, on a support, a material selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and The photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator forms a photosensitive resin composition layer; an exposure process, which exposes the photosensitive resin composition layer into a pattern; a development process, the photosensitive resin The composition layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer formation process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer formation process and the exposure process, exposure is performed. A preservation process is performed in at least one of the manufacturing process and the development process, between the developing process and the heating process, and between the heating process and the metal layer forming process. In the storage process, after the surface temperature reaches a certain temperature, the state is maintained in this state. Save for more than 5 minutes. <2> The method for manufacturing a laminated body according to <1>, wherein a storage process is performed between the exposure process and the development process. <3> The method for manufacturing a laminated body according to <2>, wherein the storage process performed between the exposure process and the development process satisfies the following formula, 5 ≦ t1 <(10 ^{-0.036 × T1 + 12.3} ) × 60 T1 It is the average surface temperature in the preservation process performed between the exposure process and the development process and the unit is K, and t1 is the time of the preservation process performed between the exposure process and the development process and the unit is minute. <4> The method for producing a laminated body according to any one of <1> to <3>, wherein a storage process is performed between the photosensitive resin composition layer forming process and the exposure process. <5> The method for manufacturing a multilayer body according to <4>, wherein the storage process performed between the photosensitive resin composition layer forming process and the exposure process satisfies the following formula, 5 ≦ t2 <(10 ^{-0.031 × T2 +10.7} ) × 60 T2 is the average surface temperature in the storage process between the photosensitive resin composition layer formation process and the exposure process and the unit is K, t2 is the photosensitive resin composition layer formation process and the exposure process The time of the save process in minutes. <6> The method for producing a laminated body according to any one of <1> to <5>, wherein a storage process is performed between a development process and a heating process. <7> The method for manufacturing a laminated body according to <6>, wherein the storage process performed between the development process and the heating process satisfies the following formula, 5 ≦ t3 <(10 ^{-0.02 × T3 + 8.0} ) × 60 T3 It is the average surface temperature in the storage process between the development process and the heating process and the unit is K, and t3 is the time of the storage process between the development process and the heating process and the unit is minute. <8> The method for producing a laminated body according to any one of <1> to <7>, wherein a storage process is performed between the heating process and the metal layer forming process. <9> The method for producing a laminated body according to any one of <1> to <8>, wherein the resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains a radical The polymerizable group or the photosensitive resin composition contains a radical polymerizable compound other than a polyimide precursor. <10> The method for producing a laminate according to any one of <1> to <9>, wherein the polyfluorene imide precursor includes a repeating unit represented by the following formula (1). Formula (1) [Chemical Formula 1] In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or The monovalent organic group <11> The method for producing a multilayer body according to <10>, wherein at least one of R ²³ and R ²⁴ in the formula (1) includes a radical polymerizable group. <12> The method for producing a laminated body according to <10> or <11>, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring. <13> The method for manufacturing a laminated body according to any one of <1> to <12>, wherein the following series of cycles are performed for more than 2 cycles, that is, sequentially on the pattern after the metal layer forming process, in order The photosensitive resin composition layer formation process, the exposure process, the development process, the heating process, and the metal layer formation process are performed, and between the photosensitive resin composition layer formation process and the exposure process, between the exposure process and the development process, and development A preservation process is performed between at least one of the manufacturing process and the heating process and between the heating process and the metal layer forming process. <14> The manufacturing method of the laminated body as described in any one of <1>-<13> which is a manufacturing method of the laminated body of a multiple-layer wiring structure. <15> A method for manufacturing an electronic component, comprising: a process for forming a photosensitive resin composition layer; and applying, on a support, a material selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and The photosensitive resin composition of the resin in the polybenzoxazole and the photopolymerization initiator forms a photosensitive resin composition layer; an exposure process, which exposes the photosensitive resin composition layer into a pattern; a development process, the photosensitive resin The composition layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer formation process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer formation process and the exposure process, exposure is performed. A preservation process is performed in at least one of the manufacturing process and the development process, between the developing process and the heating process, and between the heating process and the metal layer forming process. In the storage process, after the surface temperature reaches a certain temperature, the state is maintained in this state. Save for more than 5 minutes. <16> The method for manufacturing an electronic component according to <15>, wherein a plurality of electronic components are manufactured under the same storage process conditions. [Inventive effect]

According to the present invention, it is possible to provide a method for manufacturing a laminated body having excellent adhesion and a method for manufacturing an electronic component.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In the description of the group (atomic group) label in this specification, unrecorded and unsubstituted labels include both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, the drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for the exposure, actinic rays such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In the present specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In this specification, "(meth) acrylate" means either or both "acrylate" and "methacrylate", and "(meth) allyl" means "allyl" and "formyl" "(Meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" refers to "acryl" Or "methacryl". In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, if the expected effect of the process can be achieved, it is also included in this term. In the present specification, the solid content concentration refers to the mass percentage of components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25 ° C. In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC), and are defined as styrene conversion values. In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the protective column HZ-L, TSKgel Super HZM-M, and TSKgel Super can be used as the column. HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection was performed using a wavelength 254 nm detector using UV rays (ultraviolet rays).

<The manufacturing method of a laminated body> The manufacturing method of the laminated body of this invention is characterized by including the process of forming a photosensitive resin composition layer, and apply | coating on a support body containing the material selected from polyimide precursor, polyimide, A polybenzoxazole precursor and a photosensitive resin composition of a resin and a photopolymerization initiator in the polybenzoxazole to form a photosensitive resin composition layer; the exposure process exposes the photosensitive resin composition layer into a pattern ; A development process for developing a pattern on the photosensitive resin composition layer to form a pattern; a heating process for heating the pattern; and a metal layer formation process for forming a metal layer on the heated pattern and forming a process on the photosensitive resin composition layer And at least one of the exposure process, the exposure process and the development process, the development process and the heating process, and the heating process and the metal layer formation process, a preservation process is performed, and the preservation process is performed at the surface temperature After reaching a certain temperature, store in this state for more than 5 minutes.

According to the present invention, a laminated body having excellent adhesion can be formed. The reason why such an effect can be obtained is estimated based on the following. The film formed using the photosensitive resin composition containing the above-mentioned resin and a photopolymerization initiator tends to take time until the properties of the film become stable. It is considered that if the processing of the next process is performed in a state where the properties of the film are unstable (for example, after the photosensitive resin composition layer formation process is followed by the exposure process, etc.), a local reaction site is generated in the film. Etc., thereby applying local stress to the film. On the other hand, according to the present invention, it is considered that by providing the storage process during any of the processes described above, the properties of the film can be stabilized, and the processing of the next process can be performed while the residual stress of the film is relaxed. Therefore, it is estimated that a laminated body having excellent adhesion can be produced. The resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains a radical polymerizable group or contains a radical polymerizable property other than the polyimide precursor. In the case of the photosensitive resin composition of a compound, the effect of the present invention is particularly remarkable. Although the detailed reason is not clear, a photosensitizer containing such a radical polymerizable component (a polyimide precursor having a radical polymerizable group and a radical polymerizable compound other than the polyimide precursor) is used. In the case of a flexible resin, during the exposure process and the development process, a pattern is formed by using a cross-linking reaction of radical polymerization based on a radical polymerizable component, and the obtained pattern is heated at a high temperature during the heating process to cause fluorene imine. Chemical reaction to form a highly heat-resistant and highly insulating film. As described above, in the case where a photosensitive composition containing the radical polymerizable component is used, the reaction is multi-stage and complicated, but it is estimated that by setting the storage process described above, the microstate of the film can be stabilized and the formed film can be formed. The properties of the film are stable and a laminated body having excellent adhesion is produced. Hereinafter, each process in the manufacturing method of the laminated body of this invention is demonstrated.

(Photosensitive resin composition layer forming process) The manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer forming process which applies a photosensitive resin composition to a support body, and forms a photosensitive resin composition layer. The photosensitive resin composition will be described later.

The type of the support can be appropriately determined depending on the application. Examples include inorganic substrates, resin substrates, and resin composite substrates. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such substrates. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, and polycarbonate. Ester, polyfluorene, polyetherfluorene, polyarylate, allyl diethylene glycol carbonate, polyfluorene, polyfluorene, polyfluorene, imine, polyether, imine, polyindole, poly Fluorine resins such as phenylene sulfide, polycyclic olefins, norbornene resins, polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionic polymer resins, cyanate resins, cross-linking resins Substrates of synthetic resins such as butadiene diesters, cyclic polyolefins, aromatic ethers, maleimides, olefins, cellulose, and episulfide compounds. These substrates are rarely used directly in the above-mentioned form, and generally, depending on the form of the final product, for example, a multilayer structure such as a thin film transistor (TFT) element is formed. When the surface of the photosensitive resin composition layer or the surface of the metal layer further forms the photosensitive resin composition layer, the photosensitive resin composition layer or the metal layer becomes a support.

As a method of applying the photosensitive resin composition to the support, coating is preferred. Specific application methods include dip coating method, air knife coating method, curtain coating method, wire rod coating method, gravure coating method, extrusion coating method, spin coating method, and slit scanning. Method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method is more preferred. In the case of the spin coating method, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute. The thickness of the photosensitive resin composition layer is preferably applied so that the film thickness after exposure becomes 0.1 to 100 μm, and more preferably applied so that it becomes 1 to 50 μm. The thickness of the photosensitive resin composition layer to be formed is not necessarily uniform. For example, when a photosensitive resin composition layer is formed on a surface having irregularities, it may become a photosensitive resin composition layer having a different thickness.

In the process of forming the photosensitive resin composition layer, the photosensitive resin composition layer formed on the support may be dried. The drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and even more preferably 90 to 110 ° C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and even more preferably 3 to 7 minutes. In addition, the drying process is a process different from the storage process in the present invention.

(Exposure process) The manufacturing method of the laminated body of this invention includes the exposure process of pattern-wise exposing the said photosensitive resin composition layer. The exposure is not particularly limited as long as the photosensitive resin composition can be cured. For example, it is preferably performed at 100 to 10,000 mJ / cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8000 mJ / cm ² . The exposure wavelength can be appropriately set in a range of 190 to 1000 nm, and 240 to 550 nm is preferable.

(Developing Process) The manufacturing method of the laminated body of the present invention includes a developing process of developing a pattern on the photosensitive resin composition layer with respect to the exposed photosensitive resin composition layer. The development is performed using a developing solution. The developer can be used without particular limitation. A solvent is preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and fluorenes. About these details, the solvent demonstrated in the column of the resin composition mentioned later is mentioned. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- Methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbitol acetate Propylene glycol methyl ether and propylene glycol methyl ether acetate are more preferred, and cyclopentanone and γ-butyrolactone are more preferred.

The development time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and it can be performed at 20 to 40 ° C. After the treatment using the developing solution, processing can be further performed. It is preferable to use a solvent different from the developer when developing. For example, it is possible to perform washing using a solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

(Heating process) The manufacturing method of the laminated body of this invention includes the heating process which heats the pattern (resin layer) obtained by the development process. In the heating process, a cyclization reaction such as a polyfluorene imide precursor is performed. In addition, curing of unreacted radical polymerizable components is also performed. The maximum heating temperature (highest temperature during heating) is preferably 100 to 500 ° C, more preferably 140 to 400 ° C, and even more preferably 160 to 350 ° C. Regarding heating, it is preferred to perform the heating at a temperature increase rate of 1 to 12 ° C./minute from a temperature of 20 to 150 ° C., more preferably 2 to 10 ° C./minute, and even more preferably 3 to 10 ° C./minute. By setting the temperature increase rate to 2 ° C / min or more, it is possible to ensure high productivity while preventing the amine from being too volatilized, and by setting the temperature increase rate to 12 ° C / min or less, the stress remaining in the obtained film can be relaxed. . The temperature at the start of heating is preferably 20 to 150 ° C, more preferably 20 to 130 ° C, and even more preferably 25 to 120 ° C. The temperature at the start of heating refers to the heating temperature at the time when the process of heating to the highest heating temperature is started. For example, when the photosensitive resin composition is applied to a substrate and dried, the temperature after drying is, for example, gradually lowered from a temperature of 30 to 200 ° C. below the boiling point of the solvent contained in the photosensitive resin composition. It is better to heat up. Regarding heating, after reaching the maximum heating temperature, heating for 10 to 360 minutes is preferable, heating for 20 to 300 minutes is more preferable, and heating for 30 to 240 minutes is particularly preferable.

Heating can be performed in stages. By way of example, the temperature can be raised from 25 ° C to 180 ° C at 3 ° C / minute, left at 180 ° C for 60 minutes, and raised from 180 ° C to 200 ° C at 2 ° C / minute, and left at 200 ° C for 120 minutes. . Furthermore, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C / minute.

Regarding the heating process, from the viewpoint of preventing the decomposition of the polyimide precursor, it is preferable to carry out an inert gas such as nitrogen, helium, and argon in a low oxygen concentration environment. The oxygen concentration is preferably 50 vol ppm or less, and more preferably 20 vol ppm or less.

(Metal Layer Forming Process) The method for manufacturing a laminated body of the present invention includes a metal layer forming process of forming a metal layer on a pattern (resin layer) after heating. The metal layer is not particularly limited, and a known metal type can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are preferred, and copper is more preferred. The method for forming the metal layer is not particularly limited, and a known method can be used. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. For example, photolithography, peeling, electroplating, electroless plating, etching, printing, and a method of combining them can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography is combined with electrolytic plating are exemplified. As the thickness of the metal layer, the thickest part is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

(Surface activation treatment process) The manufacturing method of the laminated body of this invention may include the surface activation treatment process which surface-activated the at least one part of the said metal layer and the photosensitive resin composition layer. The surface activation treatment may be performed only on at least a part of the metal layer. It may be performed on at least a part of the photosensitive resin composition layer after the heating process, or may be performed on at least a part of both the metal layer and the photosensitive resin composition layer after the heating process. The surface activation treatment process usually proceeds after the metal layer formation process, but the metal resin layer may also be formed after the surface activation treatment process is performed on the photosensitive resin composition layer after the heating process. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform surface activation treatment on a part of a region of the metal layer where a photosensitive resin composition layer is formed on the surface. As described above, by subjecting the surface of the metal layer to surface activation treatment, it is possible to improve the adhesion to the photosensitive resin composition layer provided on the surface. The surface activation treatment may be performed on part or all of the photosensitive resin composition layer after the heating process. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, it is possible to improve the adhesion to the metal layer or the photosensitive resin composition layer provided on the surface subjected to the surface activation treatment. The surface activation treatment is selected from plasma treatment, corona discharge treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), based on CF ₄ / O ₂ , Etching treatment of NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment based on ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film, and the inclusion of amine groups and thiols It is preferred that the organic surface treatment agent of at least one of the compounds be impregnated with an organic surface treatment agent, mechanical roughening treatment using a brush, and plasma treatment, especially oxygen plasma treatment using oxygen as a raw material gas. When performing the corona discharge treatment, the energy is preferably 500 to 200,000 J / m ² , more preferably 1,000 to 100,000 J / m ² , and most preferably 10,000 to 50,000 J / m ² .

(Preservation process) In the method for producing a laminated body of the present invention, the photosensitive resin composition layer formation process and the exposure process, the exposure process and the development process, the development process and the heating process, and the heating process and the metal layer formation In any of the processes, a storage process is performed in which the surface temperature reaches a certain temperature and the state is stored in the state for more than 5 minutes. The above-mentioned preservation process may be performed between all the existing processes, or only in any one of the processes, or the above-mentioned preservation process may be performed. In the present invention, it is preferable that the storage process is performed in at least one of the photosensitive resin composition layer forming process and the exposure process, between the exposure process and the development process, and between the development process and the heating process. The preservation process between development processes is better. The storage process between the exposure process and the development process can further improve the adhesiveness of the photosensitive resin composition layer.

In the present invention, the storage process refers to a process in which the surface temperature is kept in this state for more than 5 minutes after the surface temperature reaches a certain temperature. Here, the surface temperature refers to a surface temperature of a to-be-processed object such as a pattern (resin layer) formed by a photosensitive resin composition layer or a photosensitive resin composition layer.

In the present invention, a certain temperature in the storage process does not refer to a specific temperature, but may have a predetermined temperature range. The fluctuation range of the surface temperature (the difference between the maximum value and the minimum value of the surface temperature) of the object to be processed during the storage process is preferably 15 ° C or lower, more preferably 10 ° C or lower, and 5 ° C or lower. When the fluctuation range of the surface temperature is within the above range, the properties of the film can be stabilized, and a laminated body having excellent adhesiveness can be easily produced.

In the present invention, the average surface temperature of the object to be processed in the storage process is preferably -30 ° C or higher, more preferably 4 ° C or higher, even more preferably 10 ° C or higher, and particularly preferably 20 ° C or higher. The upper limit is preferably below 100 ° C, more preferably below 60 ° C, even more preferably below 45 ° C, and particularly preferably below 30 ° C. In addition, the average surface temperature of a to-be-processed object means the average of the surface temperature of a to-be-processed object per hour. The storage process is performed for more than 5 minutes.

When a preservation process is performed between the exposure process and the development process (hereinafter, the preservation process is also referred to as a PED (Post Exposure Delay) process), the PED process is preferably performed under the condition that the following formula is satisfied. 5≤t1 <(10 ^{-0.036 × T1 + 12.3} ) × 60 T1 is the average surface temperature in the PED process and the unit is K, and t1 is the time of the PED process and the unit is minute.

The average surface temperature of the object to be treated in the PED process is preferably -30 to 60 ° C, more preferably 4 to 45 ° C, and even more preferably 20 to 30 ° C. The PED process is preferably performed for 5 to 720 minutes, more preferably performed for 5 to 480 minutes, and further preferably performed for 5 to 360 minutes. In the PED process, the fluctuation range of the surface temperature of the object to be treated is preferably 15 ° C or lower, more preferably 10 ° C or lower, and further preferably 5 ° C or lower.

When a storage process is performed between the photosensitive resin composition layer formation process and the exposure process (hereinafter, the storage process is also referred to as a PCD (Post Coating Delay) process), the PCD process is to satisfy the following formula: It is better to perform under the conditions. 5≤t2 <(10 ^{-0.031 × T2 + 10.7} ) × 60 T2 is the average surface temperature in the PCD process and the unit is K, and t2 is the time of the PCD process and the unit is minute.

The average surface temperature of the object to be treated in the PCD process is preferably -30 to 60 ° C, more preferably 4 to 45 ° C, and even more preferably 20 to 30 ° C. In addition, the PCD process is preferably only 5 to 360 minutes, more preferably 5 to 120 minutes, and still more preferably 5 to 60 minutes. In the PCD process, the fluctuation range of the surface temperature of the object to be treated is preferably 15 ° C or lower, more preferably 10 ° C or lower, and further preferably 5 ° C or lower.

When a preservation process is performed between the development process and the heating process (hereinafter, the preservation process is also referred to as a PDD (Post Developing Delay) process), it is preferable that the PDD process is performed under the condition that the following formula is satisfied. 5≤t3 <(10 ^{-0.02 × T3 + 8.0} ) × 60 T3 is the average surface temperature in the PDD process and the unit is K, and t3 is the time of the PDD process and the unit is minute.

The average surface temperature of the object to be treated in the PDD process is preferably 4 to 80 ° C, more preferably 10 to 60 ° C, and even more preferably 20 to 30 ° C. The PDD process is preferably performed for 5 to 1200 minutes, more preferably performed for 5 to 720 minutes, more preferably performed for 5 to 600 minutes, and particularly preferably performed for 5 to 300 minutes. In the PDD process, the fluctuation range of the surface temperature of the object to be treated is preferably 30 ° C or lower, more preferably 20 ° C or lower, and further preferably 10 ° C or lower.

When a preservation process is performed between the heating process and the metal layer formation process (hereinafter, the preservation process is also referred to as a PBD (Post Bake Delay) process), the average surface temperature of the object in the PBD process is 4 to 100 ° C is preferable, 10 to 80 ° C is more preferable, and 20 to 60 ° C is more preferable. The PBD process is preferably performed for 5 to 2400 minutes, more preferably performed for 5 to 1200 minutes, more preferably performed for 5 to 900 minutes, and particularly preferably performed for 5 to 600 minutes. In the PBD process, the fluctuation range of the surface temperature of the object to be treated is preferably 60 ° C or lower, more preferably 45 ° C or lower, and further preferably 30 ° C or lower.

The method for manufacturing a laminated body of the present invention is preferably performed in the following series of cycles of 2 or more cycles, that is, sequentially forming a photosensitive resin composition layer on the pattern (resin layer) after the metal layer forming process. Process, exposure process, development process, heating process, and metal layer formation process, and between the photosensitive resin composition layer formation process and the exposure process, between the exposure process and the development process, between the development process and the heating process, and the heating process The storage process is performed in at least one of the metal layer formation process. The cycle is preferably performed 2 to 7 times, and more preferably 2 to 5 times. This makes it possible to produce a multilayer body having a multilayer wiring structure in which a resin layer formed of a photosensitive resin composition layer and a metal layer are alternately laminated. In addition, with the increase of the number of layers, peeling is likely to occur at the interface between the metal layer and the resin layer, the interface between the resin layers, and the interface between the resin layer and the support. It does not cause peeling between layers. Therefore, the effect of the present invention can be obtained more significantly.

FIG. 1 is a diagram showing an example of a multilayer body having a multilayer wiring structure. In the figure, reference numeral 500 indicates a laminated body, reference numerals 201 to 204 indicate resin layers, and reference numerals 301 to 303 indicate metal layers. A desired pattern is formed in the resin layer 201. This pattern can be formed, for example, by negative-type development. A metal layer 301 is formed on the surface of the resin layer 201. The metal layer 301 is formed so as to cover a part of the surface of the groove 401 formed in the resin layer 201. A resin layer 202 is formed on the metal layer 301. A desired pattern is formed in the resin layer 202 and a part of the metal layer 301 is exposed on the resin layer 202. A metal layer 302 is formed on the surface of the resin layer 202. The metal layer 302 is formed so as to cover a part of the surface of the groove 402 formed in the resin layer 202, and is electrically connected to the metal layer 301 exposed to the resin layer 202. A resin layer 203 is formed on the metal layer 302. A desired pattern is formed in the resin layer 203, and a part of the metal layer 302 is exposed on the resin layer 203. A metal layer 303 is formed on the surface of the resin layer 203. The metal layer 303 is formed so as to cover a part of the surface of the groove 403 formed in the resin layer 203, and is electrically connected to the metal layer 302 exposed to the resin layer 203. A resin layer 204 is formed on the metal layer 303. A desired pattern is formed in the resin layer 204, and a part of the metal layer 303 is exposed on the resin layer 204. A part of the metal layer 302 is also exposed in the resin layer 204 in FIG. 1. The laminated body functions as an insulating film of the resin layers 201 to 204, and the metal layers 301 to 303 function as wiring layers. This laminated body can be preferably used as a redistribution layer in an electronic component.

<Photosensitive resin composition (resin composition)> Next, the photosensitive resin composition (henceforth a resin composition) used for the manufacturing method of the laminated body of this invention is demonstrated.

<< Resin> The resin composition in the present invention contains a resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. When a polyfluorene imide precursor or a polybenzoxazole precursor is used as the resin, it tends to be difficult to stabilize film properties. Therefore, when a polyfluorene imide precursor or a polybenzoxazole precursor is used as the resin, the effect of the present invention is particularly remarkable. Among them, when a polyfluorene imide precursor (preferably, a polyfluorene imide having a radical polymerizable group) is used as the resin, the effect of the present invention is particularly remarkable.

The content of the resin in the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and 70 to 99% by mass relative to the total solid content of the resin composition. % Is particularly good. The content of the resin in the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, still more preferably 60 to 99% by mass, and 70 to 99% by mass of the total solid content of the resin composition. 99% by mass is particularly good. The content of the polyimide precursor in the total mass of the resin contained in the resin composition is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. It is preferable that the resin contained in the resin composition consists essentially of polyimide. The case where the resin contained in the resin composition consists essentially of polyimide means, for example, that the content of the resin other than the polyimide precursor contained in the resin is the content of the polyimide precursor It is preferably 3% by mass or less.

(Polyimide precursor) As the polyimide precursor, a polyimide precursor containing a repeating unit represented by formula (1) is preferable. Formula (1) [Chemical Formula 2] In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred.

R ²¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aryl group, a linear or branched aliphatic group having 2 to 20 carbon atoms, and a cyclic group having 6 to 20 carbon atoms. An aliphatic group, an aryl group having 6 to 20 carbons, or a group including a combination thereof is preferable, and a group including an aryl group having 6 to 20 carbons is more preferable. Examples of the aryl group include the following.

[Chemical Formula 3] In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms, -O-, -C (= O)-, -S-, -S (= O) _2- , and-which may be substituted with a fluorine atom. NHCO- and a group thereof are preferred, and a single bond or a group selected from a C1-C3 alkylene group, -O-, -C (= O)-, -S which may be substituted by a fluorine atom The group in-, -SO ₂ -is more preferably selected from -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) ₂ -A divalent radical of-is more preferable.

Specific examples of R ²¹ include diamine residues remaining after removal of the amine group of the following diamines. Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis (aminomethyl) cyclohexane, Bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone di Amine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether And 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Hydrazone and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminediphenyl Benzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 ' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2- Bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxy Phenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diaminopara-terphenyl, 4 , 4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl ] 碸, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) Anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphosphonium, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy) 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-amino ) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone , 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'- Dimethyl-3,3'-diaminodiphenylphosphonium, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diamine Cumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2 , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1 2,2-bis (4-aminophenyl) ethane, diaminobenzidine aniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3 -Bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradefluorofluoroheptane, 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] Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-tri Fluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Methylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5- Trifluoromethylphenoxy) diphenylphosphonium, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5 , 5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least one of 2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5,5', 6,6'-hexafluorobenzidine and 4,4'-diamine tetraphenyl Diamine.

In addition, as examples of R ²¹ , diamine residues remaining after removal of the amine group of the diamines (DA-1) to (DA-18) shown below can be mentioned.

[Chemical Formula 4]

[Chemical Formula 5]

In addition, as an example of R ²¹ , a diamine residue remaining after removal of an amine group of a diamine having two or more alkylene glycol units in the main chain may be mentioned. It is preferable to combine a diamine residue containing one or more of two or more ethylene glycol chains and propylene glycol chains in one molecule, and more preferably a diamine residue containing no aromatic ring. Examples include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( The above are trade names, manufactured by HUNTSMAN Corporation), 1- (2- (2- (2-aminopropyloxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- ( 2-Aminopropoxy) propane-2-yl) oxy) propane-2-amine and the like are not limited thereto. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemical Formula 6]

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

In formula (1), R ²² represents a tetravalent organic group, a tetravalent group containing an aromatic ring is more preferred, and a group represented by the following formula (1-1) or formula (1-2) is more preferred.

Formula (1-1) [Chemical Formula 7] In the formula (1-1), R ¹¹² is a single bond or a hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO _2- , and -NHCO-, which may be substituted with a fluorine atom. And a group in a combination thereof is preferred, and a single bond or a group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -which may be substituted by a fluorine atom. The divalent group is more preferably selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S-, and -SO _The divalent group in the 2- group is further preferred.

Formula (1-2) [Chemical Formula 8]

Examples of R ²² include tetracarboxylic acid residues remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride. Specific examples thereof include tetracarboxylic acid residues remaining after removing acid anhydride groups from the following tetracarboxylic dianhydrides. Selected from pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'- Diphenylmethanetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2, 3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxo diphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic 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-fluorenetetracarboxylic dianhydride, 1,2, 4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3 -Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their carbon number 1 to 6 alkyl derivatives and Alkoxy derivative having 1 to 6 of at least one tetracarboxylic dianhydride.

Examples of R ²² include tetracarboxylic acid residues remaining after removing acid anhydride groups from the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below. [Chemical Formula 9]

From the viewpoint of the solubility with respect to the alkaline developer, it is preferable that R ²² has an OH group. More specifically, examples of R ²² include tetracarboxylic acid residues remaining after removing acid anhydride groups from the above (DAA-1) to (DAA-5).

In formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ²³ and R ²⁴ include a group including a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, and a radical polymerizable group. In the present invention, at least one of R ²³ and R ²⁴ preferably contains a radical polymerizable group. According to this aspect, the effect of the present invention tends to be more significantly obtained. Moreover, the photosensitive resin composition containing this polyfluorene imide precursor can be used suitably as a negative photosensitive resin composition. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond. Specific examples of the radical polymerizable group include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

[Chemical Formula 10]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. 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. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. methylene, octamethylene, _{dodecamethylene, -CH 2 CH (OH) CH} 2 - , ethyl stretching, stretch propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is more good. It is particularly preferred that R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethyl group.

The linear or branched alkyl group preferably has 1 to 30 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, Isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, norbornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and fluorene. Group, dicyclohexyl and pinenyl. Among them, cyclohexyl is preferred from the viewpoint of achieving high sensitivity. Examples of the aromatic group include a substituted or unsubstituted benzene ring group, a naphthalene ring group, a pentalene ring group, an indenyl ring group, a fluorene ring group, a heptene ring group, an indenene ring group, and a fluorene ring group. , Fused pentaphenyl ring group, pinene ring group, phenanthrene ring group, anthracene ring group, fused tetraphenyl ring group, fluorene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan Cyclic group, thienyl group, imidazole group, oxazole group, thiazole group, pyridine group, pyrazine group, pyrimidine group, pyridazine group, indazine group, indole group, benzene Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring , Isoquinoline ring, carbazole ring group, morphinyl ring group, acridine ring group, morpholine ring group, thienthyl ring group, chromene ring group, xanthene ring group, phenoxaline group, phenothialine group Azine ring group or phenazine ring group. A phenyl ring group is preferred.

In formula (1), when A ²² is an oxygen atom and R ²³ is a hydrogen atom and / or A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyfluorene imide precursor may be bonded to a polymer having an ethylenically unsaturated bond. Tertiary amine compounds form conjugate bases. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropylmethacrylate.

In addition, when the alkali is developed, it is preferable that the polyfluorene imide precursor has a fluorine atom in the structural unit from the viewpoint of improving the resolution. The fluorine atom can impart water repellency to the surface of the film at the time of alkali development, and can suppress infiltration from the surface. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and from the viewpoint of solubility in an alkaline aqueous solution, 20% by mass or less is preferable.

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

In order to improve the storage stability of the resin composition, it is preferable to seal the end of the main chain of the polyfluorene imide precursor with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine. Preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amine group. 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 , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

The polyfluorene imide precursor may be composed of a repeating unit represented by formula (1) and other repeating units as other polyfluorine imide precursors. When other repeating units are included, the proportion of other repeating units in the polyfluorene imide precursor is preferably 1 to 60 mole%, and more preferably 5 to 50 mole%.

The polyimide precursor in the present invention can be configured so as not to substantially contain other polyimide precursors other than the polyimide precursor containing a repeating unit represented by formula (1). The term “substantially free” means that, for example, the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 20,000 to 28,000, more preferably 22,000 to 27,000, and even more preferably 23,000 to 25,000. The dispersion degree (Mw / Mn) of the polyfluorene imide precursor is not particularly determined, but 1.0 or more is preferable, 2.5 or more is more preferable, and 2.8 or more is more preferable. The upper limit of the dispersion degree of the polyimide precursor is not particularly limited, and is preferably 4.5 or less, for example, and can be set to 3.4 or less.

(Polyimide) The polyimide used in the present invention may be a polymer compound having a fluorene imine ring, and is not particularly limited. A compound represented by the following formula (4) is preferred, The compound represented by the following formula (4) is more preferably a compound having a radical polymerizable group. Examples of the radical polymerizable group include a polymerizable group described using the polyfluorene imide precursor described above, and the preferable ranges are also the same. Formula (4) [Chemical Formula 11] In the formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When the polyfluorene imide has a radical polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2) A radical polymerizable group may be introduced at the end of the polyfluoreneimide. Formula (4-1) [Chemical Formula 12] In the formula, R ¹³³ is a radical polymerizable group, and the definition of other groups is the same as that of formula (4). Formula (4-2) [Chemical Formula 13] In the formula, at least one of R ¹³⁴ and R ¹³⁵ is a radical polymerizable group, and the other is an organic group. The definition of other groups is the same as that of formula (4).

Examples of the divalent organic group represented by R ¹³¹ include the same groups as those of R ²¹ in the formula (1) of the polyfluorene imide precursor described above, and preferred ranges are also the same. Examples of the tetravalent organic group represented by R ¹³² include the same groups as those of R ²² in the formula (1) of the polyfluorene imide precursor described above, and preferred ranges are also the same.

The polyimide has an imidization rate of 85% or more, more preferably 90% or more. The fluorene imidization rate is 85% or more, thereby reducing the shrinkage of the membrane due to the ring closure caused by the fluorene imidization by heating, and thereby suppressing the occurrence of warpage.

Polyimide not only contains repeating structural units of the above formula (4) each based on one type of R ¹³¹ or R ¹³² , but also may contain repeating units including two or more different types of R ¹³¹ or R ¹³² . In addition to the repeating unit of the formula (4) described above, the polyfluoreneimide may contain other kinds of repeating structural units.

Polyfluorene imine can be synthesized, for example, by a method in which a tetracarboxylic dianhydride is reacted with a diamine compound (a part of which is replaced by a blocking agent as a monoamine) at a low temperature, and at a low temperature. A method of reacting a tetracarboxylic dianhydride (replacement with a capping agent as an acid anhydride or a monoacid chloride compound or a monoactive ester compound) with a diamine compound, which is obtained by using a tetracarboxylic dianhydride and an alcohol A diester, which is then reacted with a diamine in the presence of a condensing agent to replace a part of it with a capping agent as a monoamine, to obtain a diester by using a tetracarboxylic dianhydride and an alcohol, and then The phosphonium carboxylic acid is chlorinated to react with a diamine (a part of which is replaced with a monoamine capping agent) and other methods to obtain a polyfluorene imine precursor, and complete it by a known fluorene imidization reaction method.方法 Imidation method or method of stopping 醯 imidization reaction and introducing 醯 imine structure locally, and then mixing the fully 醯 imidized polymer and the poly 醯 imine precursor to locally introduce 醯Of imine structure Law. Examples of commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN CORPORATION).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, a weight average molecular weight of 20,000 or more is more preferable. When two or more kinds of polyimide are contained, the weight average molecular weight of at least one kind of polyimide is preferably in the above range.

(Polybenzoxazole precursor) In the present invention, as the polybenzoxazole precursor, the structure and the like are not particularly limited, and a compound containing a repeating unit represented by the following formula (3) is preferred. Formula (3) [Chemical Formula 14] In the 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), the definitions of R ¹²³ and R ¹²⁴ are the same as those of R ²³ in formula (1), and the preferred ranges are also the same.

In the formula (3), it is preferable that the divalent organic group represented by R ¹²¹ includes at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are more preferred, and a dicarboxylic acid containing an aromatic group is more preferred. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a linear or branched (preferably linear) aliphatic group and Dicarboxylic acids composed of two COOH are more preferred. The linear or branched (preferably straight-chain) aliphatic group has a carbon number of 2 to 30, more preferably 2 to 25, more preferably 3 to 20, particularly preferably 4 to 15, and 5 to 10 Is even better. It is preferred that the linear aliphatic group is an alkylene group. Specific examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and amber. Acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid , Adipic acid, octafluoroadipate, 3-methyladipate, pimelic acid, 2,2,6,6-tetramethylpimelate, suberic acid, dodecafluorosuberic acid, nonyl Diacid, Sebacic acid, Hexafluorosebacic acid, 1,9-Azelaic acid, Dodecanedioic acid, Tridecanedioic acid, Tetradecanedioic acid, Pentadecanoic acid, Hexadecanedioic Acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosenedioic acid, behenedioic acid, behenedioedioic acid, behenedenedioic acid, twenty-four Glycanedioic acid, pentadecanedioic acid, hexacosane diacid, heptacosenedioic acid, octacosenedioic acid, icosane enedioic acid, sescanedioic acid, 31 Acid, tris dodecanedioic acid, glycol acid, and further include represented by the following formula of the dicarboxylic acid.

[Chemical Formula 15] (In the formula, Z represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6).

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid composed of only the following aromatic group and two COOH is more preferable.

[Chemical Formula 16] In the formula, A represents a member selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH ₃ ) ₂ -2-valent base in the group.

As specific examples of the dicarboxylic acid containing an aromatic group, 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether terephthalic acid are preferable.

In formula (3), R ¹²² represents a tetravalent organic group. Examples of the tetravalent organic group include groups described with R ²² in the formula (1), and preferred ranges are also the same.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and still more preferably 9200 to 11200. The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited. For example, it is preferably below 2.6, more preferably below 2.5, even more preferably below 2.4, even more preferably below 2.3, and below 2.2 Even better.

(Polybenzoxazole) The polybenzoxazole may be a compound having a benzoxazole ring, and is not particularly limited. A compound having a repeating unit represented by the following formula (X) is preferable. It is a compound represented by the following formula (X), and a compound having a radical polymerizable group is more preferable. Examples of the radically polymerizable group include radically polymerizable groups described with reference to the aforementioned polyfluorene imide precursor, and the preferred ranges are also the same. [Chemical Formula 17] In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

When the polybenzoxazole has a radical polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³³ and R ¹³⁴ as shown in the following formula (X-1) or formula (X-2) It is shown that a radical polymerizable group can be introduced into the terminal of the polybenzoxazole. Formula (X-1) [Chemical Formula 18] In the formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a radical polymerizable group, and the other is an organic group, and the definition of the other groups is the same as that of the formula (X). Formula (X-2) [Chemical Formula 19] In the formula (X-2), R ¹³⁷ is a radical polymerizable group, the others are substituents, and the definitions of other groups are the same as those of the formula (X).

Examples of the divalent organic group represented by R ¹³³ include an aliphatic group and an aromatic group. As a specific example, a group described with R ¹²¹ of the formula (3) of a polybenzoxazole precursor can be cited, and the preferred range is also the same.

Examples of the tetravalent organic group represented by R ¹³⁴ include a group described with R ¹²² in Formula (3) of a polybenzoxazole precursor, and the preferred ranges are also the same.

The polybenzoxazole may not only contain repeating structural units represented by the above formula (X) based on one kind of R ¹³³ or R ¹³⁴ , but may also contain two or more kinds of R ¹³³ or R ^{134 having} different kinds. Repeating structural unit represented by formula (X). In addition to the repeating unit of the formula (X), the polybenzoxazole may contain other types of repeating structural units.

The polybenzoxazole is obtained, for example, by reacting a diaminophenol derivative with the following compound to obtain a polybenzoxazole precursor and oxazolating it using a known oxazolation reaction method. The compound is selected Self-containing dicarboxylic acids including R ¹³³ and dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the aforementioned dicarboxylic acids. In the case of a dicarboxylic acid, in order to increase the reaction yield, an active ester-type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may 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 particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, a weight average molecular weight of 20,000 or more is more preferable. When there are two or more kinds of polybenzoxazole, the weight average molecular weight of at least one kind of polybenzoxazole is preferably in the above range.

<<< Radical Polymerizable Compound> The resin composition in the present invention may further contain a radical polymerizable compound. By containing a radically polymerizable compound, a negative photosensitive resin composition can be preferably used. Furthermore, a cured film having more excellent heat resistance can be formed. As the radical polymerizable compound, a compound having an ethylenically unsaturated bond is preferred, and a compound containing two or more groups having an ethylenically unsaturated bond is more preferred. The radical polymerizable compound may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. As the group having an ethylenically unsaturated bond, styryl, vinyl, (meth) acrylfluorenyl, and (meth) allyl are preferred, and (meth) acrylfluorenyl is more preferred. The radical polymerizable compound in the present invention is a component different from the resin. That is, a polyfluorene imide precursor having a radical polymerizable group, a polyfluorene imide having a radical polymerizable group, a polybenzoxazole precursor having a radical polymerizable group, and a radical polymerizable group Polybenzoxazole is equivalent to resin.

In the present invention, a monomer-type radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low-molecular compound, and a low-molecular compound having a molecular weight of 2,000 or less is preferred, a low-molecular compound having a molecular weight of 1500 or less is more preferred, and a low-molecular compound having a molecular weight of 900 or less is further preferred. The molecular weight of the radical polymerizable monomer is usually 100 or more. The oligomer-type radically polymerizable compound is typically a polymer having a relatively low molecular weight, and a polymer obtained by bonding 10 to 100 radically polymerizable monomers is preferred. As the molecular weight, a polystyrene-equivalent weight average molecular weight by a gel permeation chromatography (GPC) method is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000.

The number of functional groups of the radically polymerizable compound in the present invention refers to the number of radically polymerizable groups in one molecule. From the viewpoint of resolvability, it is preferable that the resin composition contains at least one type of a bifunctional or more radically polymerizable compound containing two or more radical polymerizable groups, and contains at least one type of a 2- to 4-functional radically polymerizable compound. Better.

Examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amines, and more preferably Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amines of unsaturated carboxylic acids and polyamine compounds. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an affinity substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration condensation reactants of functional or polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group or toluene Substituted reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and these contents are incorporated into this specification.

As the radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and neoopentyl glycol di (meth) acrylate. acrylate), pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, adipate Alcohols (meth) acrylates, trimethylolpropane tris (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, glycerol or trimethylolethane, etc. A compound obtained by adding (meth) acrylate to functional alcohol by adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 (Meth) acrylic acid urethanes described in Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Acrylate as epoxy tree Epoxy acrylates and (meth) acrylic acid reaction product of polyfunctional acrylate or methacrylate, and a mixture of these. The compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred.

As the radical polymerizable compound, it is also possible to use a fluorene ring described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like. Compounds of ethylenically unsaturated groups or cardo resins. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-43946, Japanese Unexamined Patent Publication No. 1-40337, Japanese Unexamined Patent Publication No. 1-40336, and specific unsaturated compounds described in Japanese Unexamined Patent Publication No. Hei 2-200 can be cited. A vinylphosphonic acid-based compound described in Japanese Patent No. 25493 and the like. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photopolymerizable monomer and oligomer.

In addition to the above, compounds represented by the following general formulae (MO-1) to (MO-5) can be preferably used. In the formula, when T is an oxyalkylene group, a carbon atom-side end is bonded to R.

[Chemical Formula 20]

[Chemical Formula 21]

In each of the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. A plurality of R and T in the molecule may be the same or different. In each of the compounds represented by the above formulae (MO-1) to (MO-5), at least one of the plurality of Rs is represented by -OC (= O) CH = CH ₂ or -OC (= O) C (CH ₃ ) = A group represented by CH ₂ . Specific examples of the compounds represented by the formulae (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779.

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-62986 as formulas (1) and (2) together with specific examples thereof can also be used as radical polymerizable compounds, which compounds are added to a polyfunctional alcohol A compound obtained by (meth) acrylated with ethylene oxide or propylene oxide. Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as radical polymerizable compounds, and these contents are incorporated into this specification.

As the radical polymerizable compound, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; Nippon Kayaku Co., Ltd. .), Dipentaerythritol hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these A structure in which the (meth) acrylfluorenyl group is bonded via an ethylene glycol residue and a propylene glycol residue is preferable. It is also possible to use their oligo type. In addition, as a preferable example, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formula (MO-1) and (MO-2) may be mentioned. It is also possible to use SR209 manufactured by Sartomer company Inc.

The radical polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. Examples of commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers produced by TOAGOSEI CO., LTD. The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the compound is in the above-mentioned range, the manufacturing and handling properties are excellent, and further the developability is excellent. Moreover, the radical polymerizability was favorable.

As the radical polymerizable compound, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, and trimethylol. Polypropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylol melamine, etc., and (meth) acrylic acid and ε-caprolactone esterified ε-hexane Lactone modified polyfunctional (meth) acrylate. Among them, a compound represented by the following formula (C) is preferable.

Formula (C) [Chemical Formula 22]

In the formula, 6 R are each a group represented by the following formula (D), or 1 to 5 of the 6 R are groups represented by the following formula (D), and the rest are represented by the following formula (D E) represents a group.

Formula (D) [Chemical Formula 23]

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bonding bond.

Formula (E) [Chemical Formula 24]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

A compound having such a caprolactone structure is commercially available, for example, as KAYARAD DPCA series by Nippon Kayaku Co., Ltd. DPCA-20 (in the formulae (C) to (E) above, m = 1, The number of groups represented by formula (D) = 2, and R ¹ is a hydrogen atom compound), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (D) = 3, R ¹ is a compound of hydrogen atom), DPCA-60 (in the above formula, m = 1, the number of groups represented by formula (D) = 6, R ¹ is a compound of hydrogen atom), DPCA-120 ( In the above formula, m = 2, the number of groups represented by formula (D) = 6, a compound in which R ¹ is a hydrogen atom), and the like.

As the radical polymerizable compound, at least one selected from the group of compounds represented by the following general formula (i) or (ii) is also preferable.

[Chemical Formula 25]

In formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and y each independently represents An integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In formula (i), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the formula (ii), the total number of (meth) acrylfluorenyl groups is five or six, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In formula (i), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferred. The total of each m is preferably an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is particularly preferable. In formula (ii), n is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferred. In addition, the total of each n is preferably an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is particularly preferable. In formula (i) or (ii),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-is the end of the oxygen atom side and X bond The shape is better. In particular, in formula (ii), a form in which all six X's are acrylfluorenyl is preferable.

Examples of commercially available compounds represented by the formulae (i) and (ii) include SR-494, Nippon Kayaku Co., which is a four-functional acrylate having four ethylene oxide chains, manufactured by Sartomer company Inc., Ltd. makes DPCA-60, which is a 6-functional acrylate having 6 pentene oxygen chains, TPA-330, which is a tri-functional acrylate having 3 isobutylene oxygen chains, and the like.

As the radically polymerizable compound, the aminomethyl compounds described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Ester acrylates, as disclosed in 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 based on a skeleton are also preferable. In addition, it is also possible to use an additive having an amine structure or a thioether structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238. Form polymerizable monomers. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd), NK ester M-40G, NK ester 4G, NK ester M-9300, NK Esters A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), And the like.

As the radical polymerizable compound, it is preferable to have a partial structure represented by the following formula from the viewpoint of heat resistance. Among them, * in the formula is a connection key.

[Chemical Formula 26]

Specific examples of the compound having the above partial structure include trimethylolpropane tri (meth) acrylate, isocyanurate ethylene oxide modified di (meth) acrylate, and isocyanurate ring. Ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc.

In the resin composition, from the viewpoint of good radical polymerizability and heat resistance, the content of the radical polymerizable compound is preferably 1 to 50% by mass based on the total solid content of the resin composition. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 30% by mass or less. The mass ratio of the resin (preferably a polyfluorene imide precursor) to the radical polymerizable compound (resin / polyimide precursor / radical polymerizable compound) is preferably 98/2 to 10/90. 95/5 to 30/70 is more preferable, and 90/10 to 50/50 is more preferable. When the mass ratio of a resin and a radically polymerizable compound is the said range, a cured film which is more excellent in hardenability and heat resistance can be formed. The radical polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

<< Photoinitiator >> The resin composition in the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator, a photoradical polymerization initiator, and the like, and a photoradical polymerization initiator is preferred. The resin composition in the present invention contains a photoradical polymerization initiator, and after the resin composition is applied to a substrate such as a semiconductor wafer to form a resin composition layer, the light is caused by the generated free radicals. It is hardened, and the solubility in a light irradiation part can be reduced. Therefore, for example, there is an advantage that by exposing the resin composition layer through a light mask having a pattern that only shields the electrode portion, it is possible to easily create regions having different solubility depending on the pattern of the electrode or the like.

The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it may be an active agent which generates a certain action with a photo-excited sensitizer and generates an active radical. 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 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) and use ethyl acetate solvent to measure at a concentration of 0.01 g / L.

As the photopolymerization initiator, a known compound can be arbitrarily used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and compounds having a trihalomethyl skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, and hexaarylbisimidazole Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like. Regarding these details, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357 and incorporate the contents into this specification. In addition, as the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-amino ketone compound, a fluorenylphosphine compound, and a metallocene compound can also be preferably used. More specifically, for example, a photopolymerization initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a photopolymerization initiator described in Japanese Patent No. 4225898 can also be used. As the α-hydroxyketone compound, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used. As the α-amino ketone compound, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As the α-amino ketone compound, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption maximum wavelength matches a wavelength light source such as 365 nm or 405 nm. Examples of the fluorenylphosphine compound include 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using an oxime compound, exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a hot alkali generator, so it is particularly preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. . Preferred oxime compounds include, for example, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3-propanyloxyimine Aminobutane-2-one, 2-acetaminoiminopentane-3-one, 2-acetaminoimino-1-phenylpropane-1-one, 2-benzidine Oxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1 -Phenylpropane-2-one and the like.

Among commercially available products, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Publication No. 2012-14052) can also be preferably used Documented photopolymerization initiator 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. DFI-091 (DAITO (Manufactured by CHEMIX Co., Ltd.). Further, an oxime compound having a fluorine atom can be used. Specific examples of such an oxime compound include the compounds described in Japanese Patent Application Laid-Open No. 2010-262028, and Japanese Patent Application No. 2014 Compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Publication No. -500852, and compounds (C-3) described in paragraph 0101 of Japanese Patent Application Laid-Open No. 2013-164471. Examples of the best oxime compound include An oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, an oxime compound having a sulfur aryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like.

As the photopolymerization initiator, from the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenylphosphine compounds. , Phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene- At least one of an iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound is preferably selected from the group consisting of a trihalomethyltriazine compound, an α-hydroxyketone compound, α -At least one of an aminoketone compound, a fluorenylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, and an acetophenone compound is more preferable At least one selected from the group consisting of trihalomethyltriazine compound, α-hydroxyketone compound, α-amino ketone compound, oxime compound, triarylimidazole dimer and benzophenone compound is further preferred, and the metallocene Compound An oxime compound is further preferred, and an oxime compound is particularly preferred.

As the photopolymerization initiator, N, N'-tetraane such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can be used. -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; quinones formed by condensation with aromatic rings such as alkyl anthraquinone; benzoin alkyl ether Benzoin compounds such as benzoin ether compounds, benzoin and alkyl benzoin; benzoin derivatives such as benzoin dimethyl ketal and the like. A compound represented by the following formula (I) can also be used. [Chemical Formula 27] 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; phenyl group; carbon number 1 to 20 alkyl groups, 1 to 12 alkoxy groups, halogen atoms, cyclopentyl, cyclohexyl, 2 to 12 alkenyl groups, and 2 to 18 carbon atoms interrupted by one or more oxygen atoms An alkyl group and a phenyl group substituted with at least one of alkyl groups having 1 to 4 carbons; or a biphenyl group, and R ⁵¹ is a group represented by formula (II), or the same group as R ⁵⁰ . R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 28] In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

As the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 10% by mass. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total thereof is preferably in the above range.

<<< polymerization inhibitor> It is preferable that the resin composition in the present invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, p-third-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6 -Third butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso -N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-third butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used.

When the resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the resin composition. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total is preferably in the above range.

<<< Photobase generator> The resin composition in this invention may contain a photobase generator. The photo-alkali generator is one that generates alkali by exposure and does not show activity under normal conditions of normal temperature and pressure. However, if the alkali (alkali substance) is generated when the electromagnetic wave is irradiated and heated as external stimulus, Specially limited. The alkali generated by exposure functions as a catalyst when the polyimide precursor is heated and hardened, and therefore it can be preferably used in a negative photosensitive resin composition.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and it can be set to a normal content. The content of the photobase generator is preferably in a range of 0.01 parts by mass or more and less than 30 parts by mass based on 100 parts by mass of the resin composition, more preferably in a range of 0.05 parts by mass to 25 parts by mass, and more preferably 0.1 part by mass. The range of -20 mass parts is more preferable.

In the present invention, a known compound can be used as the photobase generator. For example, M. Shirai, and M. Tsusunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci.Technol., 13,153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), such as complexes of transition metal compounds Those with structures such as ammonium salts, such as those whose amidine is partially potentialized by forming salts with carboxylic acids, ionic compounds, carbamate derivatives, and oxime ester derivatives whose alkali components are neutralized due to salt formation , Fluorenyl compounds, etc. Nonionic compounds in which the alkali component is potentially converted by a urethane bond or an oxime bond. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance produced by the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, and in particular, polyamines such as monoamines and diamines, and fluorene. The generated basic substance is preferably a compound having an amine group having a higher basicity. The reason for this is that the catalyst effect on the dehydration condensation reaction during the polyimide precursor of the polyimide precursor is strong, and a small amount can be added to show the catalyst effect on the dehydration condensation reaction and the like at a lower temperature. That is, since the generated alkaline substance has a large catalyst effect, the sensitivity of the appearance as a resin composition is improved. From the viewpoint of the catalyst effect, fluorene and aliphatic amine groups are preferred.

The photobase generator is preferably a photobase generator which does not contain a salt in the structure. It is preferable that the nitrogen atom in the alkali portion generated in the photobase generator has no charge. In the photobase generator, the generated base is potentially made better by using a covalent bond. The base generation mechanism is a covalent bond between an atom adjacent to the nitrogen atom of the generated base portion. Compounds which are cleaved to produce a base are more preferred. If the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so the solvent solubility is good, and the pot life is improved. For this reason, it is preferable that the amine generated from the photobase generator used in the present invention is a primary amine or a secondary amine.

In addition, for the reasons described above, it is preferable that the base generated as described above is potentially converted to a covalent bond in the photobase generator. Further, the generated base is more preferably converted to a amide bond, a urethane bond, or an oxime bond.

As the photobase generator, a photobase generator having a cinnamic acid ammonium structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, Japanese Patent Application Laid-Open No. 2006-189591, and Japan can also be used. A photobase generator having a carbamate structure described in JP 2008-247747, a oxime ester structure described in JP 2007-249013 and JP 2008-003581, Photobase generator of carbamoxime structure.

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

<<< Thermal alkali generator> The resin composition in this invention may contain a thermal alkali generator. The hot alkali generator includes a hot alkali generator selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40 ° C or higher, and at least one of anion and ammonium cation (A2) having 0 to 4 pKa1. Is better. Here, pKa1 represents the logarithmic display (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyacid. The acidic compound (A1) and the ammonium salt (A2) are those that generate a base upon heating. Therefore, the cyclization reaction of a polyimide precursor and the like can be promoted by the base generated from these compounds, and can be used at low temperatures. Cyclization of polyimide precursors and the like is performed. Moreover, even if these compounds coexist with a polyimide precursor which is cyclized and hardened by an alkali, the cyclization of the polyimide precursor or the like hardly progresses without heating, so that it can be prepared and stored stably Resin composition with excellent properties. In addition, in the present specification, an acidic compound refers to a compound having a pH value of less than 7 measured at 20 ° C using a pH meter. The solution is obtained by collecting 1 g of the compound into a container and adding 50 mL of ion-exchanged water and tetrahydrofuran. The mixed solution (mass ratio: water / tetrahydrofuran = 1/4) was stirred at room temperature for 1 hour to obtain a solution.

The alkali generating temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 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 even more preferably 165 ° C or lower. The lower limit of the alkali generation temperature is more preferably 130 ° C or more, and more preferably 135 ° C or more. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, it is difficult to generate an alkali during storage, so that a resin composition having excellent stability can be prepared. 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 polyfluorene imide precursor can be reduced. The alkali generation temperature can be measured, for example, by using differential scanning calorimetry to heat the compound to 250 ° C at 5 ° C / min in a pressure-resistant capsule, and read the peak temperature of the lowest temperature exothermic peak, and The temperature is taken as the alkali generation temperature.

The base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and a tertiary amine is more preferred. Tertiary amines are highly basic, so they can further reduce the cyclization temperature of polyfluorene imide precursors. The boiling point of the alkali generated by the hot alkali generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and most preferably 140 ° C or higher. 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 preferably 500 or less. In addition, the value of molecular weight is a theoretical value calculated | required from a structural formula.

The acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (A1) described later.

The ammonium salt (A2) is preferably an acidic compound. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base upon heating to 40 ° C or higher (preferably 120 to 200 ° C), or it may be a compound other than heating to 40 ° C or higher (preferably 120 to 200) ℃) to produce compounds other than the acidic compounds of the base.

In the present invention, the 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 through a covalent bond, and may also be provided outside the molecule of the ammonium cation, and it is preferably provided outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of the ammonium cation means a case where the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is called a counter anion. [Chemical Formula 29] In the above 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 , R ⁵ and R ⁷ may be bonded to form a ring, respectively.

In the present invention, it is preferable that the ammonium salt has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyfluorene imide precursor and the like can be cyclized at a low temperature, and the stability of the resin composition can be improved. When pKa1 is 4 or less, the stability of the hot alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyfluorene imide precursor and the like is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable for reasons of having both the stability of a salt and the thermal decomposition property. 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 higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be set as the hot alkali generator which can further improve the stability, hardenability, and developability of a resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the resin 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. It is more preferable that pKa1 is 3.5 or less, and it is more preferable that 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Among them, pKa1 represents the logarithm of the inverse of the first dissociation constant of the acid, and can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod , FC; Editor: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (Physical Identification of Organic Structures) (Author: Dawson, RMCet al; Oxford, Clarendon Press, 1959) The value recorded in. For compounds not described in these documents, the values calculated by the structural formula using software using ACD / pKa (manufactured by ACD / Labs) were used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 30] In the formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron-withdrawing group means that the substituent constant σm of Hammett represents a positive value. Among them, σm is explained in detail in Tono's general comment, "Journal of the Society of Organic Synthetic Chemistry", Vol. 23 No. 8 (1965) P.631-642. The electron-withdrawing group of the present invention is not limited to the substituents described in the aforementioned documents. Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and 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 ethenyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical Formula 31] 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 aryl group.

In the present invention, it is also preferred that the carboxylate anion is represented by the following formula (X). [Chemical Formula 32] In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenyl group, an arylene group, -NR ^X- , and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group, Alkenyl or aryl.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenylimide diacetate anion, and an oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any one of the following general formulae (Y1-1) to (Y1-6). [Chemical Formula 33]

In the above general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ R ¹⁰⁷ and R ¹⁰⁸ and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. 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.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ^108, and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. Rings can be monocyclic or polycyclic. Examples of the linking group when a ring is formed by the above-mentioned group bonding include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and combinations thereof. 2-valent link base. Specific examples of the formed ring include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, perylene ring, carbazole ring, and the like.

In the present invention, the ammonium cation is preferably a structure represented by the formula (Y1-1) or (Y1-2), and is represented by the formula (Y1-1) or (Y1-2), and R ¹⁰¹ is an aryl group. The structure is more preferred, and is represented by formula (Y1-1), and the structure where R ¹⁰¹ is an aryl group is particularly preferred. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y). [Chemical Formula 34] In formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, and n represents an integer of 1 or more.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, and an alkyl group, an alkenyl group or an aryl group is preferred. R ¹¹ and R ¹² are preferably a hydrogen atom.

R ¹³ to R ^{15 each} represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described with reference to R ¹¹ and R ¹² . R ¹³ to R ^{15 are} particularly preferably an alkyl group, and the preferred embodiments are the same as those described with R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. Rings can be monocyclic or polycyclic. Examples of the linking group when R ¹⁴ and R ^{15 are} bonded to form a ring include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The bivalent link base. Specific examples of the formed ring include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, perylene ring, carbazole ring, and the like.

Among R ¹³ to R ¹⁵ , R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms), and R ¹⁴ and R ¹⁵ are respectively An alkyl group independently having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms) is preferred. According to this aspect, it is possible to easily produce amine species having a high boiling point. From the viewpoint of the basicity or boiling point of the amine species to be generated, the total number of carbon atoms of R ¹³ , R ¹⁴ and R ¹⁵ is preferably 7 to 30, and more preferably 10 to 20. From the reason that amine species with a high boiling point are easily generated, the amount of the chemical formula of "-NR ¹³ R ¹⁴ R ¹⁵ " in the formula (Y) is preferably 80 to 2000, and more preferably 100 to 500.

Further, as an embodiment for further improving the adhesion with a metal layer such as copper, in formula (Y), R ¹³ and R ¹⁴ are methyl or ethyl groups, and R ¹⁵ is a straight chain having 5 or more carbon atoms. , Branched or cyclic alkyl, in the form of aryl. R ¹³ and R ¹⁴ are methyl groups, R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, a cyclic alkyl group having 6 to 10 carbon atoms or a phenyl group, R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is preferably a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms, or a phenyl group. By reducing the hydrophobicity of the amine species in this way, even when the amine is adhered to a metal layer such as copper, the affinity between the metal layer and polyfluorene is improved.

In the present invention, it is also preferred that the acidic compound is a compound represented by the following formula (A1). The compound is acidic at room temperature, and the carboxyl group is decarbonated or dehydrated and cyclized by heating to disappear, whereby the previously neutralized and passivated amine site becomes active, thereby becoming alkaline. Expression (A1) will be described below.

Formula (A1) [Chemical Formula 35] In Formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a mono-valent organic group, L ¹ represents a (m + 1) -valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

In the formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic group. An aromatic group is preferred. By making A ^{1 an} aromatic group, a base with a high boiling point can be easily produced at a lower temperature. By increasing the boiling point of the generated alkali, the polyimide precursor can be prevented from volatilizing or decomposing due to heating during hardening, and the polyimide precursor can be more effectively cyclized. Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, third butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl. The carbon number of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, and even more preferably from 2 to 10. The alkenyl group may be any of linear, branched, and cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group. Examples of the divalent or higher aliphatic group include a group obtained by removing one hydrogen atom from the monovalent aliphatic group. The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing a hetero atom. The aromatic group may have a substituent or may be unsubstituted. Unsubstituted is better. Specific examples of the aromatic group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indenyl ring group, a fluorenyl ring group, a heptene ring group, an indenene ring group, a fluorenyl ring group, and a condensed pentaphenyl group. Ring group, pinene ring group, phenanthrene ring group, anthracene ring group, fused tetraphenyl ring group, fluorene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene Ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring group, indazine ring group, indole ring group, benzofuran ring group Benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline Ring group, carbazole ring group, morphinyl ring group, acridine ring group, phenanthroline ring group, thienthyl ring group, benzopyran ring group, xanthene ring group, phenoxaline group, phenothiazine ring And phenazine ring, benzene ring is the best. The aromatic group may have a plurality of aromatic rings connected via a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferred. It is also preferable that the alkylene group is any of a linear chain and a branch. Specific examples of the group in which a plurality of aromatic rings are connected via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropyl, and triphenylmethane. Group, tetraphenylmethane and the like.

Examples of the substituent which may have an organic group represented by A ¹ include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and alkoxy groups such as a methoxy group, an ethoxy group, and a third butoxy group. Aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; ethoxyl, propyloxy, and Benzyloxy, such as benzyloxy; ethynyl, benzyl, isobutylfluorenyl, acrylfluorenyl, methacryl, and methoxysulfenyl; methylmercapto and tertiary butylmercapto Alkyl mercapto groups; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl groups such as methyl, ethyl, third butyl, and dodecyl; halogenated alkyl groups such as fluorinated alkyl; cyclopentyl, Cycloalkyl groups such as cyclohexyl, cycloheptyl, and adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl; hydroxyl; carboxyl; formamyl; Sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfoamido; silyl; amino; monoalkylamino; dialkylamino; aryl Group; diaryl group; sulfoxy; or combinations thereof.

L ¹ represents a (m + 1) -valent linking group. The linking group is not particularly limited, and examples include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , and alkylene (preferably having 1 carbon number) ~ 10 straight or branched alkylene), cycloalkyl (preferably a cycloalkyl having 3 to 10 carbon atoms), alkenyl (preferably a linear or branched alkylene having 210 carbon atoms) ) Or a linking base formed by connecting a plurality of them. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, an alkylene group, a linear or branched alkylene group is more preferred, a linear alkylene group is further preferred, and an ethylene group or a methylene group is particularly preferred. Methylene is the best.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group and an aromatic group. Examples of the aliphatic group and the aromatic group include those described above with reference to A ¹ . The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include the above. R ¹ is preferably a group having a carboxyl group. That is, R ¹ is preferably a group represented by the following formula. -L ² - (COOH) _n in the formula, L ² represents a (n + 1) divalent linking group, n represents an integer of 1 or more. Regarding the linking group represented by L ² , the groups described above with reference to L ¹ may be mentioned, and the preferred ranges are also the same. Ethylene or methylene is particularly preferred, and methylene is most preferred. n represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of n is the maximum number of substituents which can be used for the linking group represented by L ² . When n is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of a resin composition can be improved.

m represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can adopt. When m is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of a resin composition can be improved. p represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of p is the maximum number of substituents that can be used for the organic group represented by A ¹ . When p is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a). [Chemical Formula 36] In formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m + 1) -valent linking group, L ² represents a (n + 1) -valent linking group, m represents an integer of 1 or more, and n represents an integer of 1 or more. Integer, p represents an integer of 1 or more. The definitions of A ¹ , L ¹ , L ² , m, n, and p in the general formula (1a) are the same as those described in the general formula (A1), and the preferable ranges are also the same.

In the present invention, it is preferable that the compound represented by the formula (A1) is N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A ¹ is an aromatic group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1 in the general formula (A1). N-aryliminodiacetic acid easily produces tertiary amines with a high boiling point at 120-200 ° C.

Hereinafter, specific examples of the hot alkali generator are described, but the present invention is not limited thereto. These may be used individually or in mixture of 2 or more types. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferable, and (A-1) to (A-9), (A-18) ) ~ (A-21), (A-23), (A-24) are further preferred.

[Table 1]

[Table 2] [table 3] [Table 4] [table 5]

As the hot alkali generator used in the present invention, the compounds described in paragraphs 0015 to 0055 of the specification of Japanese Patent Application No. 2015-034388 can also be preferably used and incorporated into this specification.

When a hot alkali generator is used, the content of the hot alkali generator in the resin composition is preferably 0.1 to 50% by mass based on the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. As the hot alkali generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<<< Thermal radical polymerization initiator> The resin composition in this invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, when a cyclization reaction of a polyimide precursor is performed, a polymerization reaction such as a polymerizable compound can be performed. When the polyfluorene imide precursor contains a radical polymerizable group, the polymerization reaction of the polyfluorene imide precursor can be performed simultaneously with the cyclization of the polyfluorene imide precursor, and therefore, higher heat resistance can be achieved. Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azineium compounds, and metallocenes Compounds, active ester compounds, compounds having carbon-halogen bonds, azo compounds, and the like. Among them, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90 to 130 ° C, and more preferably 100 to 120 ° C. Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-63554 can be cited. Among commercially available products, PERBUTYL Z and PERCUMYL D (manufactured by NOF CORPORATION.) Can be preferably used.

When the resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator relative to the total solid content of the resin composition is preferably 0.1 to 50% by mass, and more preferably 0.1 to 30% by mass. 0.1 to 20% by mass is particularly preferred. The thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the polymerizable compound, and more preferably contained in an amount of 0.5 to 30 parts by mass. According to this aspect, a cured film having more excellent heat resistance is easily formed. The thermal radical polymerization initiator may be only one kind, or two or more kinds. When there are two or more types of thermal radical polymerization initiators, the total is preferably in the above range.

<<< Antirust agent> It is preferable that the resin composition in this invention contains an antirust agent. The resin composition contains a rust inhibitor, thereby effectively inhibiting metal ions originating from the metal layer (metal wiring) from moving into the resin composition layer. As the rust inhibitor, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-15701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and Japanese Patent Application Laid-Open No. 2011- Compounds described in paragraph 0052 of Japanese Patent No. 59656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520. Specific examples include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine). Compounds such as hydrazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and thiols, Hindered phenolic compounds, salicylic acid derivative compounds, hydrazine derivative compounds. Among them, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole are preferred, and 1,2,4-triazole and 1,2,3-benzotriazole 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole are more preferred, and 1H-tetrazole is most preferred. Examples of commercially available products include KEMITEC BT-C (made by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole), 1HT (made by TOYOBO CO., LTD., 1H-tetrazole), P5T (TOYOBO CO., LTD., 5-phenyl-1H-tetrazole).

When the resin composition contains a rust inhibitor, the content of the rust inhibitor is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin, and more preferably 0.2 to 5 parts by mass. The rust inhibitor may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is within the above range.

<< Silane coupling agent It is preferable that the resin composition in the present invention may contain a silane coupling agent for improving the adhesion with a metal material such as an electrode or wiring. Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Application Laid-Open No. 2014- The compounds described in paragraphs 0060 to 0061 of 191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of international publication WO2014 / 097594. As described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. As the silane coupling agent, 2-((3- (triethoxysilyl) propyl) aminomethylamidino) benzoic acid, triethoxysilylpropylmaleic acid, and the following Compounds are also preferred. In the following formula, Et represents an ethyl group. As a commercially available product, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) and the like can also be used. [Chemical Formula 37]

The silane coupling agent 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 based on 100 parts by mass of the resin. By setting the content of the silane coupling agent to 0.1 parts by mass or more, the adhesion with the metal layer of the obtainable film becomes good, and by setting the content of the silane coupling agent to 30 parts by mass or less, and The film has good heat resistance and mechanical properties. The silane coupling agent may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is within the above range.

<< Solvent> In the present invention, when the resin composition is formed into a layer by coating, it is preferable to mix the solvent with the resin composition. As the solvent, a known solvent can be arbitrarily used. Examples include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and fluorenes. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and the like. Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) ), Alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (for example, 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2- Methyloxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- 2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-oxo On behalf of ethyl butyrate. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and 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 Esters, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As a fluorene, a dimethyl sulfene is mentioned suitably.

From the viewpoint of improving the properties of the coating surface, a form in which two or more solvents are mixed is also preferable. Among them, selected from the group consisting of 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, dimethylsulfinium, ethylcarbitol acetate, butylcarbitol ethyl A mixed solution composed of two or more of an acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferable to use dimethyl sulfene and γ-butyrolactone together.

When the resin composition has a solvent, from the viewpoint of coating properties, it is preferable to set the content of the solvent to a total solid content concentration of the resin composition of 5 to 80% by mass, and more preferably 5 to 70% by mass. 10 to 60% by mass is particularly good. The solvent content may be adjusted by the desired thickness and coating method. For example, if the coating method is a spin coating method or a slit coating method, the content of the solvent having a solid content concentration in the above range is preferred. In the case of the spray coating method, the amount is preferably 0.1 to 50% by mass, and the amount is more preferably 1.0 to 25% by mass. By adjusting the amount of the solvent by the coating method, a resin composition layer having a desired thickness can be uniformly formed. The solvent may be only one kind, or two or more kinds. When there are two or more solvents, the total is preferably in the above range. From the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide The content of amidine is preferably less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.

<<< Sensitizing dye> The resin composition in this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal alkali generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like to generate effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal base generator, the photobase generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification. When the resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass relative to the total solid content of the resin composition, more preferably 0.1 to 15% by mass, and further 0.5 to 10% by mass. Better. The sensitizing dye may be used singly or in combination of two or more kinds.

<< chain transfer agent >> The resin composition in the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These can generate free radicals by supplying hydrogen to low-active radical species, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Class, etc.). When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and more preferably 100 parts by mass relative to the total solid content of the resin composition. 1 to 5 parts by mass. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is in the above range.

<<<Surfactant> From the viewpoint of improving the coating property, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred. [Chemical Formula 38]

When the resin composition contains a surfactant, the content of the surfactant relative to the total solid content of the resin composition is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind, or two or more kinds. When two or more kinds of surfactants are contained, the total thereof is preferably in the above range.

<< Higher Fatty Acid Derivatives> In order to prevent polymerization from being hindered by oxygen, a higher fatty acid derivative such as behenic acid or ammonium behenate can be added to the resin composition of the present invention after coating. Localized on the surface of the composition during drying. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition. The higher fatty acid derivative may be only one type, or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably in the above range.

<< Other additives >> As long as the effect of the present invention is not impaired, the resin composition in the present invention can be blended with various additives as required, for example, inorganic particles, hardeners, hardening catalysts, fillers, and antioxidants. , UV absorber, anti-agglomerating agent, etc. When these additives are blended, the total blended amount is preferably 3% by mass or less of the solid content of the resin composition.

<<< Restrictions on Other Contained Substances >> From the viewpoint of the properties of the coated surface, the moisture content of the resin composition in the present invention is preferably less than 5 mass%, and less than 1 mass% is more preferably, less than 0.6. The mass% is particularly good.

From the viewpoint of insulation, the metal content of the resin composition in the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Extraordinary. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably in the above range. In addition, as a method for reducing the metal impurities inadvertently contained in the resin composition, a raw material having a small metal content can be selected as a raw material constituting the resin composition, and the raw material constituting the composition of the present invention is filtered with Polytetrafluoroethylene and other methods are used to line the inside of the device and perform distillation under conditions that minimize contamination.

From the viewpoint of wiring corrosion, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, the presence of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion are in the above-mentioned ranges, respectively.

<Preparation of resin composition> A resin composition can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, for the purpose of removing foreign matters such as garbage and particles in the resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously cleaned with an organic solvent. In the filtration process of the filter, a plurality of filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times. When the filtering is performed a plurality of times, the filtering may be circular. In addition, filtration may be performed after pressurization. When the filtration is performed after the pressurization, the pressure for pressurizing is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine a filter and an impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<Electronic component> Next, an embodiment of an electronic component obtained by applying the method for manufacturing a laminated body of the present invention will be described. The electronic component 100 shown in FIG. 2 is a so-called three-dimensional mounting device, and a multilayer body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring substrate 120. In addition, in this embodiment, a case where the number of stacked layers of a semiconductor element (semiconductor wafer) is mainly described will be described. However, the number of stacked layers of a semiconductor element (semiconductor wafer) is not particularly limited. 16 floors, 32 floors, etc. It may be one floor.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 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 element.

The laminated body 101 has a structure of flip-chip bonding a semiconductor element 101a without a through electrode and semiconductor elements 101b to 101d with a through electrode 102b to 102d. That is, the electrode pad of the semiconductor element 101a without a through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b with a through electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump. The connection pad on the other side of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent to the connection pad are formed by a metal bump 103b such as a solder bump. connection. Similarly, the connection pads on the other side of the semiconductor element 101c having the through electrode 102c and the connection pads on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto are connected by metal bumps such as solder bumps. 103c and connected.

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

The laminated body 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a plurality of layers of wiring substrates using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material are used. Examples of the wiring substrate 120 to which the resin substrate is applied include a plurality of copper-clad laminated boards (multilayer printed wiring boards) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which the redistribution layer 105 is formed is arranged between the wiring substrate 120 and the multilayer body 101, and the wiring substrate 120 and the multilayer body 101 are electrically connected via the redistribution layer 105. The insulating layer 115 is formed by a method for manufacturing a laminated body according to the present invention. The insulating layer 115 may have a plurality of layers of wiring structures as shown in FIG. 1. One end of the redistribution layer 105 is connected to an electrode pad formed on a surface of the redistribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Further, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. An underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

<The manufacturing method of an electronic component> Next, the manufacturing method of the electronic component of this invention is demonstrated. The manufacturing method of the electronic component of this invention includes the manufacturing method of the laminated body of this invention mentioned above. The method for manufacturing an electronic component of the present invention is preferable to manufacture a plurality of electronic components under the same storage process conditions. [Example]

Hereinafter, the present invention will be further specifically described by examples. The present invention is not limited to the following examples without departing from the scope of the present invention. In addition, as long as there is no particular limitation, "%" and "part" are the basis of quality. NMR is short for nuclear magnetic resonance.

(Synthesis Example 1) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (P-1: Polymer without radical polymerizable group Synthesis of hydrazone imide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (drying at 140 ° C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried by molecular sieve. The suspension was heated at 100 ° C for 3 hours. After starting heating and after a few minutes, a clear solution was obtained. 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. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. The viscosity increased during the addition of SOCl ₂ . After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was added dropwise with 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 ml of N-methylpyrrolidone at 20 to 23 ° C over 20 minutes. The resulting solution. Then, the reaction mixture was stirred at room temperature for 1 ton. Next, the polyimide precursor was precipitated in 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, poured into 4 liters of water again, and stirred for 30 minutes, and then filtered again. Then, the polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (P-1) containing a repeating unit represented by the following formula. [Chemical Formula 39]

(Synthesis Example 2) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (P-2: radical-containing Synthesis of polymerizable polyfluorene imide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and the temperature was at 60 ° C. After stirring for 18 hours, a diester of pyromellitic acid and 2-hydroxyethyl methacrylate was produced. Next, the obtained diester was chlorinated with SOCl _{2 and} then converted to a polyfluorene imine precursor by 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. 1 In the same manner, a polyfluorene imide precursor (P-2) containing a repeating unit represented by the following formula was obtained. [Chemical Formula 40]

(Synthesis Example 3) [Polyimide precursor derived from 4,4'-oxybisphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (P -3: Synthesis of a polyimide precursor having a radical polymerizable group)] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride (dried at 140 ° C 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 diethylene glycol dimethyl ether, and mixed at 60 ° C It was stirred at a temperature of 18 hours for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl _{2 and} then converted to a polyfluorene imine precursor by 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. 1 In the same manner, a polyfluorene imide precursor (P-3) containing a repeating unit represented by the following formula was obtained. [Chemical Formula 41]

(Synthesis Example 4) [Synthesis of acrylic polymer (P-6)] 27.0 g (153.2 mmol) of benzyl methacrylate and 20 g (157.3 mmol) of N-isopropylmethacryl Amidine, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 mmol) and 300 g of 3-methoxy-2-propanol were mixed. In a nitrogen environment, the mixed solution was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75 ° C 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 completion of the reaction, the polymer was poured into 5 liters of water to precipitate a polymer, and the mixture was stirred at 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, and it was again poured into 4 liters of water and stirred for 30 minutes to perform filtration and removal again. Then, the obtained acrylic resin was dried at 45 ° C. for 3 days under reduced pressure to obtain an acrylic polymer (P-6) represented by the following formula. [Chemical Formula 42]

<Preparation of photosensitive resin composition> The components described below were mixed and a coating solution of the photosensitive resin composition was prepared as a uniform solution. (Composition) Resin: parts by mass of the radical polymerizable compound described in the following table: parts by mass of the photo radical polymerization initiator described in the following table: parts by mass of the silane coupling agent described in the following table: The parts by mass of the rust preventive agent described in the following table: the parts by mass of the polymerization inhibitor described in the following table: the parts by mass of the alkali generator described in the following table: the parts by mass of the solvent 1 in the following table (Dimethylmethylene): 100 parts by mass of solvent 2 (γ-butyrolactone): 25 parts by mass

[TABLE 6]

The abbreviations listed in the table are as follows. (Resin) P-1 to P-3: Polyimide precursors (P-1) to (P-3) synthesized in Synthesis Examples 1 to 3 P-5: Matrimid 5218 (manufactured by Huntsman Corporation, closed-loop type) Polyimide) P-6: Acrylic polymer (P-6) (acrylic resin) synthesized in Synthesis Example 5 P-7: Polymethylmethacrylate (Mw = 15000, Sigma-Aldrich Co . LLC.)

(Radical Polymerizable Compound) B-1: SR209 (manufactured by Sartomer company Inc., tetraethylene glycol diacrylate) B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co, Ltd., ethoxy group) Isocyanurate triacrylate) B-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co, Ltd., pentaerythritol tetraacrylate) B-4: A-DPH (manufactured by Shin-Nakamura Chemical Co, Ltd., Dipentaerythritol hexaacrylate)

(Photo radical polymerization initiator) C-1: IRGACURE OXE 01 (manufactured by BASF, oxime compound) C-2: IRGACURE OXE 02 (manufactured by BASF, oxime compound) C-3: IRGACURE-784 (manufactured by BASF, Metallocene compound) C-4: ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION, oxime compound)

(Silane coupling agent) D-1: KBM-602 (silane compound having an amine group manufactured by Shin-Etsu Chemical Co., Ltd.) D-2: 2-((3- (triethoxysilyl) Propyl) aminomethylamido) benzoic acid (silane compound with carboxyl group produced by Aquila Pharmatech LLC) D-3: triethoxysilylpropylmaleic acid (manufactured by Gelest, Inc. and carboxyl group) Silane compounds)

(Antirust agent) E-1: KEMITEC BT-C (made by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole) E-2: 1HT (made by TOYOBO CO., LTD., 1H-tetrazole ) E-3: P5T (manufactured by TOYOBO CO., LTD., 5-phenyl-1H-tetrazole)

(Polymerization inhibitor) F-1: 4-methoxyphenol F-2: p-benzoquinone F-3: 1-nitroso-2-naphthol

(Alkali generator) A-1, A-21, A-40: Compounds of the following structure (thermal alkali generator) A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photo-alkali generator). In addition, the compound is a compound that generates a base by being decomposed even when heated. That is, it is also a hot base generator.) [Chemical Formula 43]

<Production of laminated body> After each photosensitive resin composition is subjected to pressure filtration through a filter having a pore width of 0.8 μm, it is applied in a layered manner on a silicon wafer by a spin coating method and used. The hot plate was dried at 100 ° C for 5 minutes to form a photosensitive resin composition layer. Next, the storage process (PCD process) was performed at the time and temperature shown in the following table, and then the photosensitive resin composition layer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ / cm ² . . Next, the exposed photosensitive resin composition layer was subjected to a storage process (PED process) at the times and temperatures described in the following table, and then developed using cyclopentanone for 60 seconds to form holes having a diameter of 10 μm. Next, after the storage process (PDD process) was performed at the time and temperature shown in the following table, the resin layer (pattern) was formed by heating at 230 ° C for 3 hours under a nitrogen environment. Next, the heated resin layer (pattern) was cooled to room temperature, and after the storage process (PBD process) was performed at the time and temperature shown in the following table, a copper plating process was performed to form copper with a thickness of 5 μm on the resin layer. Thin film, thereby forming a laminated body 1. In addition, each storage process was performed by leaving it in a clean thermostat-hygrostat (manufactured by ESPEC CORP., PCR-3J) adjusted to the set temperature described in the following table. Next, the copper thin film of the laminated body 1 was irradiated with oxygen plasma, and then the photosensitive resin composition was applied, exposed, developed, heated, and each storage process was performed. Then, copper plating was performed to form a 5 μm-thick copper thin film on the resin layer. And laminated body 2 was obtained. Next, the copper thin film of the laminated body 2 was irradiated with oxygen plasma, and then the photosensitive resin composition was applied, exposed, developed, heated, and each storage process was performed. Then, a copper plating treatment was performed to form copper having a thickness of 5 μm on the resin layer. A thin film was obtained to obtain a laminated body 3.

[TABLE 7]

The storage time in each condition described in the above table is the elapsed time after the surface temperature reaches the set temperature. The fluctuation range of the surface temperature during each storage process is 5 ° C or less. The average surface temperature in each storage process is approximately the same as the set temperature.

<Evaluation> [Peeling Defect (Evaluation 1)] The multilayer body 2 was cut in the vertical direction and a cross section with a width of 5 mm was observed to confirm the presence or absence of peeling between the resin layer / resin layer and the copper / resin layer. If peeling does not occur. It means that it has excellent adhesion and has a better result. A: No peeling occurred B: 1 to 2 peelings occurred C: 3 to 5 peelings occurred D: 6 or more peelings occurred

[Peeling failure (Evaluation 2)] The multilayer body 3 was cut in the vertical direction and a cross section with a width of 5 mm was observed to confirm the presence or absence of peeling between the resin layer / resin layer and the copper / resin layer. If peeling does not occur. It means that it has excellent adhesion and has a better result. A: No peeling occurred B: 1 to 2 peelings occurred C: 3 to 5 peelings occurred D: 6 or more peelings occurred

[Limiting Resolution (Evaluation 3)] The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). The exposure was performed using i-rays, and the exposure was performed at a wavelength of 365 nm with an exposure energy of 200 mJ / cm ² up to 5 μm to 25 μm using a light mask of a fuse box in 1 μm increments. The exposed photosensitive resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developing solution. Specifically, cyclopentanone was spray-coated on the exposed photosensitive resin composition layer, and then propylene glycol methyl ether acetate was spray-coated for development for 60 seconds. The line width of the silicon wafer exposed at the bottom of the fuse box was evaluated by the following criteria. The smaller the line width, the smaller the width of the metal wiring that can be formed in the subsequent plating process, and the better the result. The measurement limit is 5 μm. The results are shown in the table. A: 5 μm or more and 8 μm or less B: 8 μm or more and 10 μm or less C: 10 μm or more and 15 μm or less D: 15 μm or more

[TABLE 8]

As shown in the above table, in the examples in which the storage process was performed, a laminated body having excellent adhesiveness could be produced. In addition, the photosensitive resin composition using the polyimide precursor composition 1 to 12 as the resin has high limit resolution, and Examples 1 to 33, 36, and 37 using the photosensitive resin composition are used. The laminated body can further reduce the width of the metal wiring.

100‧‧‧Electronic components

101a ～ 101d‧‧‧Semiconductor element

101‧‧‧Laminated body

102b ～ 102d‧‧‧through electrode

103a ～ 103e‧‧‧ metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ Insulation

120‧‧‧ wiring board

120a‧‧‧ surface electrode

201 ～ 204‧‧‧Resin layer

301 ～ 303‧‧‧metal layer

401 ～ 403‧‧‧slot

500‧‧‧layer

FIG. 1 is a schematic diagram showing a configuration of an embodiment of a laminated body. FIG. 2 is a schematic diagram showing a configuration of an embodiment of an electronic component.

Claims (16)

A method for manufacturing a laminated body, comprising: a process for forming a photosensitive resin composition layer, and applying on a support body a material selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzo The photosensitive resin composition of the resin in the oxazole and the photopolymerization initiator forms a photosensitive resin composition layer; an exposure process, which exposes the photosensitive resin composition layer into a pattern; a development process, the photosensitive resin composition The object layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer forming process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer forming process and the exposure process The storage process is performed in at least one of the exposure process and the development process, the development process and the heating process, and the heating process and the metal layer forming process. At least one of the storage process is performed at the surface temperature. After reaching a certain temperature, store in this state for more than 5 minutes. The method for manufacturing a laminated body according to item 1 of the scope of patent application, wherein the storage process is performed between the exposure process and the development process. The method for manufacturing a laminated body according to item 2 of the scope of patent application, wherein the aforementioned storage process performed between the aforementioned exposure process and the aforementioned development process satisfies the following formula, 5 ≦ t1 <(10 ^{-0.036 × T1 + 12.3} ) × 60 T1 is the average surface temperature in the storage process performed between the exposure process and the development process and the unit is K, and t1 is the time and unit of the storage process performed between the exposure process and the development process For minutes. The method for manufacturing a laminated body according to item 1 or item 2 of the scope of the patent application, wherein the storage process is performed between the photosensitive resin composition layer forming process and the exposure process. The application of the method of manufacturing a laminate in item 4 patentable scope of the body, wherein the forming of the storage process is performed between the process and the exposure process to the photosensitive resin composition layer satisfies the following formula, 5≤t2 <(10 ^{- 0.031 × T2 + 10.7} ) × 60 T2 is the average surface temperature in the storage process performed between the photosensitive resin composition layer forming process and the exposure process, and the unit is K, and t2 is the photosensitive resin composition The time and unit of the aforementioned storage process between the layer formation process and the aforementioned exposure process is in minutes. The method for manufacturing a laminated body according to item 1 or 2 of the scope of patent application, wherein the storage process is performed between the development process and the heating process. The method for manufacturing a laminated body according to item 6 of the scope of the patent application, wherein the aforementioned storage process performed between the aforementioned development process and the aforementioned heating process satisfies the following formula, 5 ≦ t3 <(10 ^{-0.02 × T3 + 8.0} ) × 60 T3 is the average surface temperature in the storage process performed between the development process and the heating process and the unit is K, and t3 is the time and unit of the storage process performed between the development process and the heating process For minutes. The method for manufacturing a laminated body according to item 1 or 2 of the scope of application for a patent, wherein the storage process is performed between the heating process and the metal layer forming process. The method for manufacturing a laminated body according to item 1 or item 2 of the scope of patent application, wherein the resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor includes radical polymerization. Or the photosensitive resin composition contains a radical polymerizable compound other than the polyfluorene imide precursor. The method for manufacturing a laminated body according to item 1 or item 2 of the scope of patent application, wherein the aforementioned polyimide precursor includes a repeating unit represented by the following formula (1), where formula (1) In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group. The method for manufacturing a laminated body according to item 10 of the scope of patent application, wherein in the formula (1), at least one of R ²³ and R ²⁴ includes a radical polymerizable group. The method for producing a laminated body according to item 10 of the scope of patent application, wherein R ²² in the aforementioned formula (1) is a tetravalent group containing an aromatic ring. According to the manufacturing method of the laminated body described in the first or second scope of the patent application, the following series of cycles are performed for more than two cycles, that is, the aforementioned photosensitivity is sequentially performed on the pattern after the aforementioned metal layer forming process. The photosensitive resin composition layer formation process, the exposure process, the development process, the heating process, and the metal layer formation process, and between the photosensitive resin composition layer formation process and the exposure process, the exposure process, and the development The storage process is performed among at least one of the manufacturing process, the development process and the heating process, and the heating process and the metal layer forming process. The method for manufacturing a multilayer body according to item 1 or 2 of the scope of patent application, which is a method for manufacturing a multilayer body with a plurality of layers of wiring structure. An electronic component manufacturing method includes: a photosensitive resin composition layer forming process, and applying on a support body a material selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzo The photosensitive resin composition of the resin in the oxazole and the photopolymerization initiator forms a photosensitive resin composition layer; an exposure process, which exposes the photosensitive resin composition layer into a pattern; a development process, the photosensitive resin composition The object layer is developed to form a pattern; a heating process to heat the pattern; and a metal layer forming process to form a metal layer on the heated pattern; and between the photosensitive resin composition layer forming process and the exposure process The storage process is performed in at least one of the exposure process and the development process, the development process and the heating process, and the heating process and the metal layer forming process. At least one of the storage process is performed at the surface temperature. After reaching a certain temperature, store in this state for more than 5 minutes. The method for manufacturing an electronic component according to item 15 of the scope of patent application, wherein a plurality of electronic components are manufactured under the same conditions of the aforementioned storage process.