TWI825000B - Film manufacturing method, laminate manufacturing method, and electronic component manufacturing method - Google Patents

Abstract

The present invention provides a method of manufacturing a laminate excellent in adhesiveness and a method of manufacturing an electronic component. In this manufacturing method, a resin composition containing a polyimide precursor and a silane coupling agent having a reactive group is used to form a resin composition layer on a support, and the resin composition layer is processed in multiple stages of two or more stages. Heating is performed, and the second stage heating is performed at a temperature higher than the heating temperature in the first stage.

Description

Film manufacturing method, laminate manufacturing method, and electronic component manufacturing method

The present invention relates to a method of manufacturing a film, a method of manufacturing a laminated body, and a method of manufacturing an electronic component.

Polyimide is used in insulation layers of electronic components due to its heat resistance and insulation properties. In addition, polyimide has low solubility in solvents, so it is also carried out by applying the precursor (polyimide precursor) before the cyclization reaction to a support or the like and then heating it to convert the polyimide into a solvent. The imine precursor is cyclized to form a hardened film.

For example, Patent Documents 1 and 2 describe manufacturing a patterned cured film using a resin composition containing a polyimide precursor. [Prior art documents] [Patent documents]

[Patent Document 1] U.S. Patent No. 9159547 [Patent Document 2] Japanese Patent Application Publication No. 2013-160827

However, the adhesion between the support and the metal layer of a film obtained using a resin composition containing a polyimide precursor is insufficient. In particular, it was found that when a plurality of resin layers and metal layers formed using a resin composition containing a polyimide precursor are alternately stacked to form a laminate, the adhesion between the resin layers increases as the number of stacked layers increases. , the adhesion between the resin layer and the metal layer is easily reduced. Furthermore, even in the films obtained by the methods described in Patent Documents 1 and 2, the adhesion to the support, the metal layer, etc. is insufficient.

An object of the present invention is to provide a method for manufacturing a film, a method for manufacturing a laminated body, and a method for manufacturing an electronic component that have excellent adhesion to a support, a metal layer, or the like.

Based on the above problems, the inventor conducted research and found that a resin composition containing a polyimide precursor and a silane coupling agent with a reactive group is used to form a resin composition layer on a support in more than two stages. By heating the resin composition layer in multiple stages, a film with excellent adhesiveness can be produced, thus solving the above problems. The present invention provides the following. <1> A method for manufacturing a film, which uses a resin composition containing a polyimide precursor and a silane coupling agent having a reactive group to form a resin composition layer on a support, using a plurality of processes in two or more stages The resin composition layer is heated in one stage, and the second stage is heated at a temperature higher than the heating temperature in the first stage. <2> The method for manufacturing a film according to <1>, wherein the resin composition is a photosensitive resin composition, and after the resin composition layer is exposed and developed to form a pattern, the film is patterned in two or more stages. The resin composition layer is heated. <3> The method for producing a film according to <1> or <2>, wherein the heating in the first stage is performed at a temperature of 130 to 170°C for 10 to 60 minutes. <4> The method for producing a film according to any one of <1> to <3>, wherein the second-stage heating is performed at a temperature of 180 to 250°C for 60 to 300 minutes. <5> The method for producing a film according to any one of <1> to <4>, wherein the reactive group of the silane coupling agent is selected from the group consisting of an acid group, an amine group, and a group having an ethylenically unsaturated bond. At least one of group and cyclic ether group. <6> A method for manufacturing a laminated body, including the method for manufacturing a film according to any one of <1> to <5>. <7> The method for manufacturing a laminated body according to <6>, wherein the process of manufacturing a film by the method for manufacturing a film according to any one of <1> to <5> is repeated two or more times. <8> The manufacturing method of the laminated body according to <6> or <7>, which further includes a process of forming a metal layer. <9> The method for manufacturing a laminated body according to any one of <6> to <8>, wherein the method for manufacturing a film according to any one of <1> to <5> is used; The process of forming a metal layer on the film is alternately performed two or more times. <10> A method of manufacturing an electronic component, including the method of manufacturing a film according to any one of <1> to <5> or the method of manufacturing a laminated body according to any one of <6> to <9> . [Effects of the invention]

According to the present invention, it is possible to provide a method of manufacturing a film, a method of manufacturing a laminated body, and a method of manufacturing an electronic component that have excellent adhesion to a support, a metal layer, or the like.

The description of the constituent elements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Among the labels for groups (atomic groups) in this specification, the labels that do not record substituted or unsubstituted include both groups without substituents and groups with substituents. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). As long as "exposure" in this specification is not particularly limited, in addition to exposure using light, drawing using particle beams such as electron beams and ion beams is also included in the exposure. In addition, the light used for exposure generally includes actinic rays or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams, represented by the bright line spectrum of a mercury lamp and excimer laser. In this specification, the numerical range expressed by "～" means a range including the numerical values written before and after "～" as the lower limit and the upper limit. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "methacrylate". "(meth)acrylic acid" means both or any one of "acrylic acid" and "methacrylic acid", "(meth)acrylyl" means "acrylyl" "base" and "methacrylyl" or both or any one of them. In this specification, the term "process" is not only an independent process, but also is included in this term if it can achieve the expected effect of the process even if it cannot be clearly distinguished from other processes. In this specification, the solid content concentration refers to the mass percentage of components other than the solvent relative to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration refers to the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC) and defined as styrene-converted values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and as the column, a guard column HZ-L, TSKgel Super HZM-M, or TSKgel Super can be used. HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent will be measured using THF (tetrahydrofuran). In addition, unless otherwise stated, detection is performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays).

<Method for Manufacturing a Membrane> The method for manufacturing a membrane of the present invention is characterized by forming a resin composition layer on a support using a resin composition containing a polyimide precursor and a silane coupling agent having a reactive group, and The resin composition layer is heated in more than one stage, and the second stage is heated at a temperature higher than the heating temperature in the first stage.

According to the present invention, a film having excellent adhesion to a support and the like can be produced. The detailed reason why this effect is obtained is uncertain, but it is presumed to be based on the following. It is considered that during the first stage of heating, the silane coupling agent interacts with the hydroxyl groups on the support to perform a coupling reaction, and the reactive groups of the silane coupling agent interact with the polyimide precursor to form bonds, etc. . Furthermore, by heating in the second stage, the polyimide precursor is cyclized to form polyimide. As a result, it is estimated that a film having excellent adhesion to a support or the like can be produced.

In the present invention, heating in each stage may have a prescribed temperature range. In the present invention, the resin composition layer can be heated in multiple stages of three or more. However, after the reaction between the silane coupling agent and the polyimide precursor, the cyclization of the polyimide precursor can be easily performed. Considering the reason for further improving the adhesion due to chemical reaction (polyimide formation reaction), it is better to conduct heating in two stages. In addition, in the present invention, when the resin composition layer is heated in two or more stages, it means that the heating in each stage is performed in a series of procedures. That is, when the resin composition layer is once cooled after being heated, or is reheated after performing any treatment, the reheating is not included in the second stage of heating in the present invention.

In the film manufacturing method of the present invention, a photosensitive resin composition is used as the resin composition, and a resin composition layer (photosensitive resin composition layer) formed on a support using the resin composition is exposed and developed. After forming the pattern, it is preferable to heat the resin composition layer in the above-mentioned multiple stages. Examples of the photosensitive resin composition include a resin composition containing a component having a radically polymerizable group and a photoreinforceable compound. Examples of the component containing a radical polymerizable group include a polyimide precursor having a radical polymerizable group, a radical polymerizable compound other than a polyimide precursor, and the like. These details will be described in the column of the resin composition described later.

The method for producing the film of the present invention will be described in detail below.

The manufacturing method of the film of the present invention includes a resin composition layer forming process using a resin composition including a polyimide precursor and a silane coupling agent having a reactive group to form a resin composition layer on a support. The resin composition will be described later.

The type of support can be appropriately determined depending on the use. Examples include inorganic substrates, resin substrates, resin composite material substrates, and the like. Examples of inorganic substrates include glass substrates, quartz substrates, silicon substrates, silicon nitride substrates, and composite substrates in which molybdenum, titanium, aluminum, copper, etc. are vapor-deposited on these substrates. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, poly Carbonate, polystyrene, polyetherstyrene, polyarylate, allyl diethylene glycol carbonate, polyamide, polyimide, polyamide imine, polyether imine, polyindole, Polyphenylene sulfide, polycyclic olefin, norbornene resin, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate ester resin, cross-linking Substrates for synthetic resins such as fumarate diester, cyclic polyolefin, aromatic ether, maleimide, olefin, cellulose, and episulfide compounds. These substrates are rarely used directly in the above-mentioned form, and are usually formed into a plurality of layered structures such as thin film transistor (TFT) devices according to the form of the final product. In addition, when a resin composition layer is further formed on the surface of the resin composition layer or the surface of the metal layer, the resin composition layer or the metal layer becomes a support.

As a method of applying the resin composition to the support, coating is preferred. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the resin composition layer, the 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, for example. Regarding the thickness of the resin composition layer, the coating is preferably performed so that the film thickness after heating becomes 0.1 to 100 μm, and more preferably the coating is applied so that the film thickness becomes 1 to 50 μm. In addition, the thickness of the formed resin composition layer may not necessarily be uniform. For example, when a resin composition layer is formed on a surface having unevenness, the resin composition layer may have different thicknesses.

In the resin composition layer forming process, the 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 further preferably 90 to 110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and further preferably 3 to 7 minutes.

In the film manufacturing method of the present invention, when a photosensitive resin composition is used as the resin composition to form the resin composition layer, the resin composition layer can be exposed and developed to form a pattern. That is, it may include an exposure process of pattern-like exposure of the resin composition layer and a development process of developing the exposed resin composition layer to form a pattern.

In the exposure process, the exposure of the resin composition layer is preferably performed with an exposure energy of 100 to 10000 mJ/cm ² at a wavelength of 365 nm, and more preferably 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190 to 1000 nm, and 240 to 550 nm is preferred.

In the development process, it is preferable to use a developer to develop the resin composition layer. As a developer, it can be used without particular restriction. Solvent is preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfur dioxide. Examples of these details include solvents described in the column of the resin composition described below. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Methyl oxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, Propylene glycol methyl ether and propylene glycol methyl ether acetate are preferred, and cyclopentanone and γ-butyrolactone are even more preferred.

The development time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited and can be performed at 20 to 40°C. After using the developer, it can then be rinsed. It is better to use a different solvent than the developer when rinsing. For example, a solvent contained in the resin composition can be used for flushing. The optimal flushing time is 5 seconds to 1 minute.

The film manufacturing method of the present invention includes a heating process of heating the resin composition layer. In this heating process, the resin composition layer is heated in two or more stages, and the second stage is heated at a temperature higher than the heating temperature in the first stage. When the exposure process and the development process have been performed, the above-mentioned heating process is performed on the resin composition layer after the development process. When the exposure process and development process are not performed (when no pattern is formed), the above-mentioned heating process is performed on the resin composition layer formed in the resin composition layer forming process.

In the present invention, the heating temperature in the first stage of heating is preferably 130 to 170°C. The lower limit of the heating temperature is preferably 140°C or higher, and more preferably 145°C or higher. The upper limit of the heating temperature is preferably 160°C or lower, more preferably 155°C or lower. In addition, the heating time in the first stage of heating is preferably 10 to 60 minutes. The lower limit of the heating time is preferably 20 minutes or more, and more preferably 25 minutes or more. The upper limit of the heating time is preferably 50 minutes or less, more preferably 40 minutes or less.

The average heating temperature in the first stage of heating is preferably 130 to 170°C. The lower limit is preferably 140°C or higher, and more preferably 145°C or higher. The upper limit is preferably 160°C or lower, and more preferably 155°C or lower. In addition, the average value of the heating temperature is the average value of the heating temperature per hour.

The temperature fluctuation range in the first stage of heating is preferably 20°C or less, more preferably 10°C or less, and further preferably 5°C or less. According to this aspect, the effect of improving the adhesive force can be expected. Here, the temperature fluctuation range during the first-stage heating is a value obtained by subtracting the minimum temperature from the maximum temperature during the first-stage heating. For example, when the first-stage heating is performed by changing the range of 145 to 155°C, the temperature variation range is 10°C. In addition, when the first stage of heating is performed at a certain temperature (for example, 150°C), the temperature fluctuation range is 0°C.

The heating in the second stage is performed at a temperature higher than the heating temperature in the first stage (preferably it is a temperature higher than 10°C or more, more preferably a temperature higher than 20°C or more, further preferably a temperature higher than 30°C or more). . In addition, when the heating temperature in the first stage of heating has a temperature fluctuation range, the second stage of heating is performed at a temperature higher than the maximum temperature in the first stage of heating (preferably a temperature higher than 10°C or more, more preferably The temperature is preferably at least 20°C, more preferably at least 30°C).

The heating temperature and heating time in the second stage of heating can be appropriately set depending on the type of polyimide precursor and the like. For example, when using a polyimide precursor with a low cyclization temperature, it is preferable to set the heating temperature to a lower low temperature. In addition, when using a polyimide precursor with a fast cyclization speed, it is better to set the heating time to be shorter. Specifically, the heating temperature in the second stage of heating is preferably 180 to 250°C. The lower limit of the heating temperature is preferably 190°C or higher, and more preferably 200°C or higher. The upper limit of the heating temperature is preferably 240°C or lower, more preferably 235°C or lower. In addition, the heating time in the second stage of heating is preferably 60 to 300 minutes. The lower limit of the heating time is preferably 120 minutes or more, and more preferably 150 minutes or more. The upper limit of the heating time is preferably 240 minutes or less, more preferably 210 minutes or less.

The average heating temperature in the second stage of heating is preferably 180 to 250°C. The lower limit is preferably 190°C or higher, and more preferably 200°C or higher. The upper limit is preferably 240°C or lower, and more preferably 235°C or lower.

The temperature fluctuation range in the second stage of heating is preferably 20°C or less, more preferably 10°C or less, and further preferably 5°C or less. According to this aspect, the mechanical properties of the obtained cured film are stable, and stable adhesive force can be easily obtained. Here, the temperature fluctuation range during the second-stage heating is a value obtained by subtracting the minimum temperature from the maximum temperature during the second-stage heating.

In the present invention, when the resin composition layer is heated in n stages with more than three extremes, the heating in the n-th stage may be performed at a temperature higher than the heating temperature in the n-1-th stage, or may be performed at a temperature higher than the heating temperature in the n-th stage. -The heating temperature of the first stage is carried out at a low temperature. Here, n is an integer of 3 or more. In addition, when the heating temperature in the n-1-th stage heating has a temperature fluctuation range, the n-th stage heating may be performed at a temperature higher than the average value of the heating temperatures in the n-1-th stage, or may be performed at a temperature higher than the average value of the heating temperatures in the n-1 stage. The heating temperature in the n-1th stage is performed at a temperature where the average value is lower.

Regarding the heating process, from the perspective of preventing the decomposition of the polyimide precursor, it is better to conduct it in an environment with a low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm by volume or less, and more preferably 20 ppm by volume or less.

After the heating process is completed, it is better to cool down. The cooling rate is preferably 1 to 5°C/min.

<Resin composition> Next, the resin composition used in the film manufacturing method of the present invention will be described.

<<Polyimide precursor>> The resin composition in the present invention contains a polyimide precursor. As the polyimide precursor, a polyimide precursor including a repeating unit represented by formula (1) is preferred. 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 1-valent organic base.

A ²¹ and A ²² each independently represent an oxygen atom or -NH-, with an oxygen atom being 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 aliphatic group having 6 to 20 carbon atoms. An aliphatic group, an aryl group having 6 to 20 carbon atoms, or a group containing a combination thereof is preferred, and a group including an aryl group having 6 to 20 carbon atoms is more preferred. Examples of the aryl group include the following.

[Chemical formula 2] In the formula, A is a single bond or a hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -and- NHCO-, and the groups in their combinations are preferably single bonds or selected from alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S The group in -, -SO ₂ - is more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C (CF ₃ ) ₂ -, -C (CH ₃ ) ₂ - Among them, the 2-valent base is further preferred.

Specifically, examples of R ²¹ include diamine residues remaining after removing 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'-diaminobiphenyl ether And 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Turquoise and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide 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-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) Phenyl) terine, bis(4-amino-3-hydroxyphenyl) terine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, Bis[4-(4-aminophenoxy)phenyl]terine, bis[4-(3-aminophenoxy)phenyl]terine, bis[4-(2-aminophenoxy)benzene base] cyclohexane, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-di Aminodiphenyl terine, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminobenzene) methyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4, 4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydranthracene, 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)fluoride, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2 , 7-diaminofluoride, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, ester 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)tetradecafluoroheptane, 2,2-bis[4-(3-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) base)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane Fluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4, 4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsine, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsine, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy) ) phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamine biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobiphenyl and 4 , at least one diamine in 4'-diaminotetraphenyl.

Examples of R ²¹ include the diamine residues remaining after removal of the amine groups of the diamines (DA-1) to (DA-18) shown below.

[Chemical formula 3]

[Chemical formula 4]

Examples of R ²¹ include the diamine residue remaining after removal of the amine group of a diamine having two or more alkylene glycol units in the main chain. Preferably, a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both is combined in one molecule, and more preferably, a diamine residue containing no aromatic ring is used. 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-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-( 2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but are not limited to these. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemical formula 5]

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

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

Formula (1-1) [Chemical Formula 6] In formula (1-1), R ¹¹² is a single bond or a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO- , and the groups in their combinations are preferably single bonds or selected from alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ - 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. A divalent group in the group of _2- is further preferred.

Formula (1-2) [Chemical Formula 7]

Examples of R ²² include the tetracarboxylic acid residue remaining after removing the acid anhydride group from tetracarboxylic dianhydride. Specific examples include the tetracarboxylic acid residue remaining after removing the acid anhydride group from the following tetracarboxylic dianhydride. Selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-Diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'- Diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2, 3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic 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-perylenetetracarboxylic dianhydride, 1,2, 4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3 -Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride and their carbon numbers At least one tetracarboxylic dianhydride among alkyl derivatives with 1 to 6 carbon atoms and alkoxy derivatives with 1 to 6 carbon atoms.

Moreover, as an example of ^R22 , the tetracarboxylic acid residue which remains after removing an acid anhydride group from the tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below is also mentioned. [Chemical formula 8]

From the viewpoint of solubility in an alkali developer, it is preferable that R ²² has an OH group. More specifically, examples of R ²² include the tetracarboxylic acid residue remaining after removing the acid anhydride group from the above-mentioned (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 linear or branched alkyl group, a cyclic alkyl group, an aromatic group, a radical polymerizable group, and the like. In the present invention, it is preferred that at least one of R ²³ and R ²⁴ contains a radically polymerizable group. According to this aspect, the effects of the present invention tend to be obtained more significantly. Moreover, the photosensitive resin composition containing this polyimide precursor can be suitably used as a negative photosensitive resin composition. Examples of radically polymerizable groups include groups having an ethylenically unsaturated bond. Specific examples of the radically polymerizable group include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like.

[Chemical formula 9]

In 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. Preferable examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecylmethylene, -CH ₂ CH (OH) CH ₂ -, ethylidene, propylene, trimethylene, -CH ₂ CH (OH) CH ₂ - are more good. A combination in which R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylidene group is particularly preferred.

The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30. 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, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. base, dicyclohexyl and pinenyl (pinenyl). Among these, cyclohexyl is preferable from the viewpoint of both high sensitivity and high sensitivity. Examples of the aromatic group include substituted or unsubstituted phenyl ring group, naphthyl ring group, pentenyl ring group, indenyl ring group, azulenyl ring group, heptaphenyl ring group, indenyl ring group, and perylene ring group. , fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, sulfenyl ring, triphenyl ring, fluorenyl ring, biphenyl ring, pyrrole ring, 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, indolazine ring group, indole ring group, benzene Furan ring group, benzothiophene ring group, isobenzofuran ring group, quinazine ring group, quinoline ring group, phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group , isoquinoline ring base, carbazole ring base, phenanthridine ring base, acridine ring base, phenanthroline ring base, thianthrene ring base, chromene ring base, xanthene ring base, phenanthienyl ring base, phenanthene ring base oxazine ring group or phenanthroline ring group. Phenyl ring group is preferred.

In formula (1), when A ²² is an oxygen atom and R ²³ is a hydrogen atom and/or when A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyimide precursor can be combined with one 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-dimethylaminopropyl methacrylate.

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

In addition, in order to improve the adhesion with 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)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

In addition, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain end of the polyimide precursor with an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride 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-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene 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, etc. Two or more types of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

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

The polyimide precursor in the present invention can also be configured to contain substantially no polyimide precursor other than the polyimide precursor containing the repeating unit represented by formula (1). Substantial absence means that, for example, the content of the other polyimide precursors contained in the resin composition is 3 mass % or less of the content of the polyimide precursors.

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 further preferably 23,000 to 25,000. The dispersion degree (Mw/Mn) of the polyimide precursor is not particularly determined, but it is preferably 1.0 or more, more preferably 2.5 or more, and still more preferably 2.8 or more. The upper limit of the dispersion degree of the polyimide precursor is not particularly limited, but for example, 4.5 or less is preferred, and it can also be 3.4 or less.

The content of the polyimide precursor in the resin composition is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, and further preferably 60 to 99% by mass relative to the total solid content of the resin composition. , 70-99% by mass is particularly good.

<<Other resin components>> The resin composition in the present invention may contain other resins within the scope that does not deviate from the gist of the present invention. Examples of other resins include polybenzoxazole precursors, polyimide, and polybenzoxazole. Furthermore, in the present invention, it is possible to substantially not contain resins other than the polyimide precursor. Substantial absence means that, for example, the content other than the polyimide precursor contained in the resin composition is 3 mass % or less of the content of the polyimide precursor.

<<Silane coupling agent>> The resin composition in the present invention contains a silane coupling agent having a reactive group. The silane coupling agent is preferably a silane compound having a reactive group, and more preferably an alkoxysilane compound having a reactive group. As the reactive group, a group showing affinity by interacting or forming a bond with the polyimide precursor is preferred. Examples include acidic groups, amine groups, groups with ethylenically unsaturated bonds, hydroxyl groups, mercapto groups, urea groups, thioether groups, isocyanate groups, etc., acidic groups, amine groups, groups with ethylenically unsaturated bonds, and rings. An ether group is preferred.

Examples of the acidic group include a carboxyl group, a sulfo group, a phosphate group, and the like, with a carboxyl group being preferred. Examples of the amino group include groups represented by -NR ¹ R ² or -N=CR ³ R ⁴ . R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ³ and R ⁴ each independently represent an alkyl group or an aryl group. The number of carbon atoms of the alkyl group represented by R ¹ to R ⁴ is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the aryl group represented by R ¹ to R ⁴ is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acrylyl group, and the like. Examples of the cyclic ether group include an epoxy group, an oxetanyl group, and the like, with an epoxy group being preferred.

In the present invention, the silane coupling agent is preferably a compound represented by the following formula (S-1). [Chemical formula 10] In the above formula, R ^S1 represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6. In addition, the alkyl group may be any of straight chain, branched, and cyclic, and straight chain is preferred. In the above formula, R ^S2 represents an alkyl group or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6. In addition, the alkyl group may be any of straight chain, branched, and cyclic, and straight chain is preferred. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. In the above formula, R ^S3 represents a reactive group. The details of the reactive group are the same as the above ranges, and the preferred ranges are also the same. In the above formula, L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, -O-, -S-, -C(=O)-, -COO-, and -NR. -, -CONR-, -OCO-, -SO-, -SO ₂ - and connecting groups that connect two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group or an aryl group. The number of carbon atoms in the alkylene group is preferably 1 to 30. The upper limit is preferably 25 or less, and further preferably 20 or less. The lower limit is more preferably 2 or more, and further more preferably 3 or more. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the aryl group is more preferably 6 to 20, and further preferably 6 to 12. In the above formula, a represents an integer of 1 to 3, b represents an integer of 1 to 3, and the total of a and b is 4 or less.

Examples of the silane coupling agent having a reactive group include 2-((3-(triethoxysilyl)propyl)aminomethyl)benzoic acid and triethoxysilylpropylma Lesamide, 2-((3-(trimethoxysilyl)propyl)aminoformyl)benzoic acid, trimethoxysilylpropylmaleamide, vinyltrimethoxy Silane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methoxysilane Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Cyloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N -2-(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-oxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Silyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl Hydrochloride of 3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercapto Propylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

Furthermore, examples include the following silane coupling agents having carboxyl groups. In the following structural formula, Me represents a methyl group, and Et represents an ethyl group. [Chemical formula 11]

As a commercially available silane coupling agent, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane), KBE-502 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloylmethyldiethoxysilane) KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-shrink Glyceryl ether propyl trimethoxysilane), KBE-803 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyl trimethoxysilane), etc.

The content of the silane coupling agent is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The lower limit is preferably 0.2 mass% or more, more preferably 0.4 mass% or more, further preferably 0.5 mass% or more, and particularly preferably 1 mass% or more. The upper limit is preferably 5 mass% or less, more preferably 4 mass% or less, further preferably 3 mass% or less, and particularly preferably 2.5 mass% or less. If the content of the silane coupling agent is within the above range, a film having excellent adhesion to a metal layer or a support can be easily formed. The content of the silane coupling agent is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polyimide precursor. The lower limit is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, and still more preferably 1 part by mass or more. The upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3.5 parts by mass or less. If the content of the silane coupling agent is within the above range, a film having excellent adhesion to a metal layer or a support can be easily formed. There may be only one type of silane coupling agent, or two or more types of silane coupling agents may be used. When two or more types are used, the total amount is preferably within the above range.

<<Radically polymerizable compound>> The resin composition in the present invention may further contain a radically polymerizable compound. By containing a radically polymerizable compound, a cured film with more excellent heat resistance can be formed. Furthermore, pattern formation can be performed by photolithography. As the radically 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 radically polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof. As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth)acrylyl group and a (meth)allyl group are preferred, and a (meth)acrylyl group is more preferred. In addition, the radically polymerizable compound in the present invention is a component different from the above-mentioned polyimide precursor and silane coupling agent.

In the present invention, the monomer-type radically polymerizable compound (hereinafter also referred to as a radically polymerizable monomer) is a compound different from the polymer compound. The radically 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 1,500 or less is more preferred, and a low molecular compound having a molecular weight of 900 or less is further preferred. In addition, the molecular weight of the radically polymerizable monomer is usually 100 or more. Moreover, the oligomer type radically polymerizable compound is typically a polymer with a relatively low molecular weight, and a polymer in which 10 to 100 radically polymerizable monomers are bonded is preferred. The molecular weight is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000 as a weight average molecular weight in terms of polystyrene calculated by gel permeation chromatography (GPC).

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

Examples of the radically 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 amides, and preferred ones are Esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, the addition reaction product of an unsaturated carboxylic acid ester or amide having an affinity substituent such as a hydroxyl group, an amino group, or a mercapto group, and a monofunctional or multifunctional isocyanate or epoxy, or a monofunctional isocyanate or epoxy can be preferably used. Dehydration condensation reaction products of functional or polyfunctional carboxylic acids, etc. In addition, the addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides with releasable 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 group of compounds substituted by unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, the description 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 radically polymerizable compound, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, and neopentyl glycol di(meth)acrylate (Neopentyl glycol di(meth)acrylate). acrylate), Pentaerythritol (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diacrylate Alcohol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl)isocyanurate, glycerol or trimethylolethane, etc. A compound in which ethylene oxide or propylene oxide is added to a functional alcohol and then (meth)acrylated, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho 50-6034, Japanese Patent Publication No. Sho 51-37193 (Meth)acrylic urethanes described in Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and polyesters described in Japanese Patent Publication No. 52-30490 Acrylates, polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred.

As the radically polymerizable compound, those described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. and having a fluorine ring and containing two or more can also be used. Compounds with ethylenically unsaturated bond groups or cardo resins. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, Japanese Patent Publication No. 1-40336, and Japanese Patent Publication No. 2-40336 can also be cited. Vinylphosphonic acid-based compounds described in Publication No. 25493, etc. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

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

[Chemical formula 12]

[Chemical formula 13]

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

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-62986 can also be used as radically polymerizable compounds. The compounds are added to polyfunctional alcohols. A compound formed by (meth)acrylation of 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 as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available: KAYARAD D-310; Nippon Kayaku Co., Ltd. .), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these The structure in which the (meth)acrylyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. Their oligomer types can also be used. Preferable examples include pentaerythritol derivatives and/or dipentaerythritol derivatives of the above formula (MO-1) and formula (MO-2). In addition, SR209 manufactured by Sartomer Company Inc. can also be used.

The radically 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 polybasic acid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. A 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 above-mentioned compound is within the above range, the production and workability are excellent, and the developability is excellent. Moreover, the radical polymerizability is good.

As the radically 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. Examples thereof include trimethylolethane, ditrimethylolethane, and trimethylol. Epsilon-hydroxypropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and other polyols are esterified with (meth)acrylic acid and ε-caprolactone. Caprolactone modified multifunctional (meth)acrylate. Among them, the compound represented by the following formula (C) is preferable.

Formula (C) [Chemical Formula 14]

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

Formula (D) [Chemical Formula 15]

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

Formula (E) [Chemical Formula 16]

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

Compounds having such a caprolactone structure are commercially available as the KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example, and examples include DPCA-20 (in the above formulas (C) to (E), m=1, The number of groups represented by formula (D) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (D) = 3, A compound in which R ¹ is a hydrogen atom), DPCA-60 (in the above formula, m=1, the number of groups represented by formula (D) = 6, a compound in which R ^{1 is a hydrogen atom), DPCA-120 (a compound in which R 1} is a hydrogen atom), DPCA-120 ( In the above formula, m=2, the number of groups represented by formula (D)=6, ^R1 is a compound in which all hydrogen atoms are present), etc.

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

[Chemical formula 17]

In formula (i) and formula (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)acrylyl group, a hydrogen atom or a carboxyl group. In the formula (i), the total number of (meth)acrylyl groups is 3 or 4, 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 formula (ii), the total number of (meth)acrylyl groups is 5 or 6, n each independently represents an integer of 0 to 10, and the total number of n is an integer of 0 to 60. However, when the total of n's is 0, any one of X is a carboxyl group.

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

Examples of commercially available products of compounds represented by formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethylene oxide chains, manufactured by Sartomer Company Inc. and Nippon Kayaku Co., Ltd. Ltd. DPCA-60, which is a hexafunctional acrylate with six amyloxy chains, and TPA-330, which is a trifunctional acrylate with three isobutylene oxygen chains, etc.

As the radical polymerizable compound, aminomethyl is described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acid ester acrylates, those with ethylene oxide described 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 having a skeleton are also preferred. In addition, additives having an amino group structure or a thioether structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 105238 can also be used. into polymerizable monomers. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

From the viewpoint of heat resistance, the radically polymerizable compound preferably has a partial structure represented by the following formula. Among them, * in the formula is the connecting key.

[Chemical formula 18]

Specific examples of the compound having the above partial structure include trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid ring Oxyethane modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, tetrahydroxymethylmethane 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 relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. It is more preferable that the upper limit is 30% by mass or less. In addition, the mass ratio of the polyimide precursor and the radically polymerizable compound (polyimide precursor/radically polymerizable compound) is preferably 98/2 to 10/90, and 95/5 to 30/70 is more preferable, and 90/10 to 50/50 is still more preferable. If the mass ratio of the polyimide precursor and the radically polymerizable compound is within the above range, a cured film with more excellent curing properties and heat resistance can be formed. Only one type of radically polymerizable compound may be used, or two or more types of radically polymerizable compounds may be used. When two or more types are used, the total amount is preferably within the above range.

<<Photopolymerization initiator>> The resin composition in the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include photocationic polymerization initiators, photoradical polymerization initiators, and the like, and photoradical polymerization initiators are preferred. The resin composition in the present invention contains a photoradical polymerization initiator. After the resin composition is applied to a substrate such as a semiconductor wafer to form a resin composition layer, light is irradiated to cause polymerization caused by the generated free radicals. Hardening can reduce the solubility in the light irradiation part. Therefore, for example, there is an advantage that regions having different solubilities can be easily produced according to the pattern of the electrodes or the like by exposing the resin composition layer through a photomask having a pattern that only shields the electrode portion.

The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator that is photosensitive to light from an ultraviolet region to a visible region is preferable. Alternatively, it may be an active agent that interacts with a photo-excited sensitizer to generate active free radicals. 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 using a known method. For example, it is preferable to measure using a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and compounds having a trihalomethyl skeleton), acylphosphine compounds such as acylphosphine oxide, and hexaarylbisazoles. , 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, organoboron compounds, iron aromatic hydrocarbon complexes, etc. Regarding these details, you can refer to the description in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification. Examples of ketone compounds include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, and this content is incorporated into this specification. Among commercially available products, KAYACUREDETX (manufactured by Nippon Kayaku Co., Ltd.) can be preferably used.

As the photopolymerization initiator, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds and metallocene compounds can also be preferably used. More specifically, for example, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the 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-aminoketone compound, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As the α-aminoketone compound, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption maximum wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used. Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF Corporation) can be used. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

As a photopolymerization initiator, an oxime compound is more preferable. By using oxime compounds, exposure latitude can be increased more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a thermal base generator. As specific examples of the oxime compound, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-80068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166 can be used. . Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, and 3-propyloxyiminobutan-2-one. Aminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminopentan-1-one, 2-benzoyl Oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-2-one, etc.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-14052 Photopolymerization initiator 2) described in the Gazette No. 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 also be used. Also, DFI-091 (DAITO CHEMIX Co., Ltd.). Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028 and Japanese Patent Application Publication No. 2014 - Compounds 24, 36 to 40 described in paragraph 0345 of Publication No. 500852, compound (C-3) described in paragraph 0101 of Japanese Patent Application Laid-Open No. 2013-164471, etc. Examples of optimal oxime compounds include An oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, an oxime compound having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like.

The photopolymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds from the viewpoint of exposure sensitivity. , phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- At least one of iron complexes and salts thereof, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds is preferred, and is selected from trihalomethyltriazine compounds, α-hydroxyketone compounds, α - At least one of an amino ketone compound, a hydroxyphosphine 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 preferred , at least one selected from the group consisting of trihalomethyltriazine compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds is further preferred, and metallocene Compounds or oxime compounds are further preferred, and oxime compounds are particularly preferred.

In addition, as the photopolymerization initiator, N,N'-tetrakanes such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michelone) can also be used. Benzyl-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 condensing aromatic rings such as alkyl anthraquinones; benzoin alkyl ethers, etc. Benzoin ether compounds, benzoin, alkyl benzoin and other benzoin compounds; benzoyl derivatives such as benzoyl dimethyl ketal, etc. Moreover, the compound represented by the following formula (I) can also be used. [Chemical formula 19] In formula (I), R ⁵⁰ is an alkyl group with 1 to 20 carbon atoms; an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group with 1 to 12 carbon atoms; phenyl; carbon number Alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, halogen atoms, cyclopentyl groups, cyclohexyl groups, alkenyl groups with 2 to 12 carbon atoms, and alkenyl groups with 2 to 18 carbon atoms interrupted by one or more oxygen atoms. Alkyl group and phenyl group substituted by at least one alkyl group having 1 to 4 carbon atoms; or biphenyl group, 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 20] In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ⁵⁴ in the above formula (I).

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

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one type, or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

<<Polymerization inhibitor>> The resin composition in the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -Tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso -N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO2015/125469 can also be used.

When the resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the resin composition. There may be only one type of polymerization inhibitor, or two or more types of polymerization inhibitors may be used. When there are two or more polymerization inhibitors, the total amount is preferably within the above range.

<<Photobase generator>> The resin composition in the present invention may contain a photobase generator. Photobase generators are those that generate bases by exposure and do not show activity under normal conditions of normal temperature and pressure. However, if they generate bases (alkaline substances) when electromagnetic wave irradiation and heating are used as external stimuli, they are not active. Specially limited. The alkali generated by exposure functions as a catalyst when the polyimide precursor is cured by heating, and therefore can be suitably used in a negative photosensitive resin composition.

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

In the present invention, known compounds can be used as the photobase generator. For example, M. Shirai, and M. Tsunooka, 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 transition metal compound complexes , those having structures such as ammonium salts, ionic compounds in which the amidine part is latent by forming a salt with carboxylic acid, ionic compounds in which the base component is neutralized by forming a salt, urethane derivatives, and oxime ester derivatives , acyl compounds and other non-ionic compounds in which alkali components are latent through urethane bonds or oxime bonds. In addition, it is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The alkaline substance generated by the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, particularly polyamines such as monoamines and diamines, amidines, and the like. It is preferred that the alkaline substance produced is a compound with an amine group having a higher basicity. The reason for this is that it has a strong catalytic effect on the dehydration condensation reaction in the imidization of the polyimide precursor, and a small amount can be added to exhibit the catalytic effect in the dehydration condensation reaction at a lower temperature. That is, the generated alkaline substance has a large catalytic effect, so the sensitivity of the appearance of the resin composition is improved. From the viewpoint of the above-mentioned catalyst effect, amidine and aliphatic amine groups are preferred.

The photobase generator is preferably one that does not contain a salt in its structure. It is preferred that there is no charge on the nitrogen atom of the base portion generated in the photobase generator. In photobase generators, the generated base is potentially optimized through the use of covalent bonds. The base generating mechanism is a covalent bond between atoms adjacent to the nitrogen atom of the generated base moiety. Compounds that generate bases upon cleavage are more preferred. If the photobase generator does not contain a salt in its 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 by the photobase generator used in the present invention is a primary amine or a secondary amine.

In addition, for the reasons described above, among the photobase generators, it is preferable that the base generated as described above is latent using a covalent bond. In addition, it is better to use amide bonds, urethane bonds, and oxime bonds to make the generated base latent.

As the photobase generator, photobase generators having a cinnamic acid amide structure described in Japanese Patent Application Publication No. 2009-80452 and International Publication No. WO2009/123122, Japanese Patent Application Publication No. 2006-189591 and Japan The photobase generator having a urethane structure described in Japanese Patent Application Publication No. 2008-247747, the photobase generator having an oxime ester structure described in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581, Photobase generator with methylcarbamate oxime structure.

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

<<Thermal base generator>> The resin composition in the present invention may contain a thermal base generator. The thermal base generator includes at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40° C. or above, and an ammonium salt (A2) of an anion having a pKa1 of 0 to 4 and an ammonium cation. For better. Here, pKa1 represents the logarithmic display of the dissociation constant (Ka) of the first proton of the polybasic acid (-Log ₁₀ Ka). The above-mentioned acidic compound (A1) and the above-mentioned ammonium salt (A2) generate a base when heated. Therefore, the base generated by these compounds can promote the cyclization reaction of the polyimide precursor and the like, and can be used at low temperatures. Perform cyclization of polyimide precursors, etc. In addition, even if these compounds coexist with polyimide precursors and the like that are cyclized and hardened by a base, cyclization of the polyimide precursors and the like hardly proceeds without heating, so it is possible to prepare storage-stable compounds. Resin composition with excellent properties. In addition, in this specification, an acidic compound refers to a compound whose pH value is less than 7 when measured at 20°C using a pH meter. The solution is to collect 1 g of the compound into a container and add 50 mL of ion-exchange water and tetrahydrofuran. The mixture (mass ratio: water/tetrahydrofuran = 1/4) was stirred at room temperature for 1 hour.

The alkali generation 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 less, still more preferably 180°C or less, and still more preferably 165°C or less. The lower limit of the alkali generation temperature is more preferably 130°C or higher, and still more preferably 135°C or higher. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120°C or higher, alkali is less likely to be generated during storage, and therefore a resin composition with excellent stability can be prepared. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200°C or lower, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature can be measured, for example, by heating the compound to 250°C at 5°C/min in a pressure-resistant capsule using differential scanning calorimetry, reading the peak temperature of the heat generation peak at the lowest temperature, and dividing the peak value into Temperature acts as a base production temperature.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. The tertiary amine has high alkalinity, so it can further reduce the cyclization temperature of the polyimide precursor. In addition, the boiling point of the base generated by the thermal base generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher. In addition, the molecular weight of the generated base is preferably 80 to 2,000. It is better if the lower limit is 100 or more. It is better if the upper limit is below 500. In addition, the molecular weight value is a theoretical value calculated based on the structural formula.

The acidic compound (A1) preferably contains one or more compounds selected from the group consisting of ammonium salts and compounds represented by the formula (A1) described below.

The above-mentioned 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 when heated to 40°C or higher (preferably 120 to 200°C), or may be a compound that is heated to 40°C or higher (preferably 120 to 200°C). ℃) compounds other than acidic compounds that generate bases.

In the present invention, the ammonium salt refers to a salt of an ammonium cation and anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or may be present outside the molecule of the ammonium cation, preferably outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded through a covalent bond. Hereinafter, the extramolecular anion in the cation part is called a counteranion. [Chemical formula 21] In the above formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ in the formula represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be bonded respectively to form a ring.

In the present invention, the ammonium salt preferably has an anion and an ammonium cation with pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still more preferably 3.2 or less. A lower limit of 0.5 or more is more preferable, and a lower limit of 1.0 or more is still more preferable. If the pKa1 of the anion is in the above range, the polyimide precursor or the like can be cyclized at low temperature, thereby improving the stability of the resin composition. When pKa1 is 4 or less, the stability of the thermal base generator is good, generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If pKa1 is 0 or more, the generated base will not be easily neutralized, and the cyclization efficiency of the polyimide precursor or the like will be good. The type of anion is preferably one selected from the group consisting of carboxylate anions, phenol anions, phosphate anions, and sulfate anions, and carboxylate anions are more preferred because they have both stability and thermal decomposability of salts. That is, the ammonium salt is more preferably a salt of ammonium cation and carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be a thermal base generator that can further improve the stability, curability and developability of the 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 further more preferable that it is 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 reciprocal of the first dissociation constant of the acid, and can be referred to Determination of Organic Structures by Physical Methods (authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod , F. C.; Editors: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955), Data for Biochemical Research (Physical Identification of Organic Structures) (Authors: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) The value recorded in . For compounds not described in these documents, values calculated based on structural formulas using software 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 22] In formula (X1), EWG represents an electron-withdrawing group.

In the present invention, the electron-withdrawing group refers to one in which Hammett's substituent constant σm represents a positive value. Among them, σm is described in detail in Yuhio Tsuno's general introduction, "Journal of the Society of Synthetic Organic Chemistry", Volume 23, No. 8 (1965), P. 631-642. In addition, the electron-withdrawing group of the present invention is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include a CF ₃ group (σm=0.43), a CF ₃ CO group (σm=0.63), a HC≡C group (σm=0.21), and a CH ₂ =CH group (σm =0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 23] 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. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The alkyl group may be any one of straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. As a substituent, a carboxyl group is preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenyl group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. As a substituent, a carboxyl group is preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. As a substituent, a carboxyl group is preferred.

In the present invention, the carboxylate anion is preferably represented by the following formula (X). [Chemical formula 24] In the formula (X), L ¹⁰ represents a single bond or a divalent connecting group selected from an alkylene group, ^an alkenylene group, an aryl group, ^-NR alkenyl or aryl.

The number of carbon atoms in the alkylene group represented by L ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. The alkylene group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. The carbon number of the alkenylene group represented by L ¹⁰ is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenylene group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. The carbon number of the aryl group represented by L ¹⁰ is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below.

The number of carbon atoms in the alkyl group represented by ^R The alkyl group may be any one of straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. The number of carbon atoms in the alkenyl group represented by ^R The alkenyl group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below. The number of carbon atoms in the aryl group represented by ^R The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below.

Specific examples of carboxylate anions include maleate anions, phthalate anions, N-phenyliminodiacetate anions, and oxalate anions. These can be used better.

The ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6). [Chemical formula 25]

In the above general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represents a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represents 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 ¹⁰¹ represents an n-valent organic group. Examples of the monovalent organic group include an alkyl group, an alkylene group, an aryl group, and the like. Examples of the divalent or higher organic group include those in which one or more hydrogen atoms are removed from a monovalent organic group and become an n-valent group. R ¹⁰¹ is preferably an aryl group. Specific examples of the aryl group include those described below with Ar ¹⁰ .

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group. As the hydrocarbon group represented by R ¹⁰² to R ¹¹¹ , R ¹⁵⁰ and R ¹⁵¹ , an alkyl group, an alkenyl group or an aryl group is preferred. The alkyl group, alkenyl group and aryl group may have a substituent. Examples of the substituent include substituents that may have an organic group represented by A ¹ described below.

The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The alkyl group may be any one of straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenyl group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The alkenyl group may have a substituent or may be unsubstituted. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted.

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 aliphatic rings (non-aromatic hydrocarbon rings), aromatic rings, heterocyclic rings, and the like. The ring can be a single ring or multiple rings. Examples of the linking group when the above-mentioned groups are bonded to form a ring include -CO-, -O-, -NH-, divalent aliphatic groups, divalent aryl groups, and combinations thereof. 2 price link base. Specific examples of the ring formed 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. ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, etc.

In the present invention, the ammonium cation is preferably a structure represented by formula (Y1-1) or formula (Y1-2), represented by formula (Y1-1) or formula (Y1-2), and R ¹⁰¹ is an aryl group The structure represented by formula (Y1-1) is particularly preferred, and the structure in which 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 26] In formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represents 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.

Ar ¹⁰ represents an aromatic group. Specific examples of the aromatic group include substituted or unsubstituted phenyl ring group, naphthyl ring group, pentadienyl ring group, indenyl ring group, azurenyl ring group, heptapenyl ring group, and indenenyl ring group. , perylene ring base, fused pentaphenyl ring base, acenaphthylene ring base, phenanthrenyl ring base, anthracenyl ring base, fused tetraphenyl ring base, cyclohexyl ring base, triphenyl ring base, fluorenyl ring base, biphenyl ring base, 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, indolazine ring group, indole Ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinolazine ring group, quinoline ring group, phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxal Oxazoline ring base, isoquinoline ring base, carbazole ring base, phenanthridine ring base, acridine ring base, phenanthroline ring base, thianthrene ring base, benzopyran ring base, xanthene ring base, phenanthrene ring base thiophene ring group, phenylthiazine ring group and phenylthiazine ring group. Among them, from the viewpoint of storage stability and high sensitivity, a phenyl ring group, a naphthyl ring group, an anthracene ring group, a phenyl ring group or a carbazole ring group is preferred, and a phenyl ring group or a naphthyl ring group is the most preferred. . Examples of substituents that the aromatic group may have include substituents that may have an organic group represented by A ¹ described below.

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

The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and Octyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group (cycloalkyl group) may be a single-ring cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cycloalkyl group include adamantyl, norbornyl, bornyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, and camphenyl. (camphoroyl), dicyclohexyl and pinenyl (pinenyl). Among them, the cyclohexyl group is the best from the viewpoint of coexistence with high sensitivity. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenyl group may be straight chain, branched, or cyclic. Straight chain or branched is preferred, and straight chain is more preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12.

R ¹³ to R ¹⁵ represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described above with R ¹¹ and R ¹² . R ¹³ to R ¹⁵ are particularly preferably alkyl groups, and preferred aspects 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 cyclic aliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring, and the like. The ring can be a single ring or multiple rings. Examples of the linking group when R ¹⁴ and R ¹⁵ are bonded to form a ring include -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups, and combinations thereof. Among them, there are 2 price connecting bases. Specific examples of the ring formed 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. ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, etc.

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 It is preferably an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, amine species with a high boiling point can be easily generated. Furthermore, from the viewpoint of the basicity or boiling point of the amine species produced, 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. In addition, since amine species with high boiling points are easily generated, the chemical formula weight of "-NR ¹³ R ¹⁴ R ¹⁵ " in formula (Y) is preferably 80 to 2000, and more preferably 100 to 500.

In addition, as an embodiment for further improving the adhesion with a metal layer such as copper, formula (Y) can be cited, in which R ¹³ and R ¹⁴ are methyl or ethyl, and R ¹⁵ is a straight line having 5 or more carbon atoms. Chain, branched or cyclic alkyl group, in the form of aryl group. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is preferably a linear alkyl group with 5 to 20 carbon atoms, a branched alkyl group with 6 to 17 carbon atoms, a cyclic alkyl group with 6 to 10 carbon atoms, or a phenyl group. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is more 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 thus reducing the hydrophobicity of the amine species, even when the amine is adhered to a metal layer such as copper, the affinity between the metal layer and polyimide or the like can be improved.

In the present invention, the acidic compound is also preferably a compound represented by the following formula (A1). The compound is acidic at room temperature, and upon heating, the carboxyl group disappears through decarbonation or dehydration cyclization, whereby the previously neutralized and passivated amine site becomes active and thus becomes alkaline. Formula (A1) will be explained below.

Formula (A1) [Chemical Formula 27] In formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent 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 formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include aliphatic groups, aromatic groups, etc., with aromatic groups being preferred. By using A ¹ as an aromatic group, a base with a high boiling point can be easily generated at a lower temperature. By raising the boiling point of the generated base, the volatilization or decomposition of the polyimide precursor due to heating during hardening can be suppressed, and the cyclization of the polyimide precursor can be performed more effectively. Examples of the monovalent aliphatic group include an alkyl group, an alkenyl group, and the like. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, tert-butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and the like. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include vinyl, (meth)allyl, and the like. Examples of the bivalent or higher aliphatic group include a group obtained by removing one hydrogen atom from the above-mentioned monovalent aliphatic group. The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing heteroatoms. 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 naphthyl ring group, a pentenyl ring group, an indenyl ring group, an azulenyl ring group, a heptadenyl ring group, an indenyl ring group, a perylene ring group, and a fused pentaphenyl group. Ring group, acenaphthylene ring group, phenanthrenyl ring group, anthracenyl ring group, fused tetraphenyl ring group, cyclohexanyl ring group, triphenyl ring group, fluorenyl 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, indolazine ring group, indole ring group, benzofuran ring group , benzothiophene ring group, isobenzofuran ring group, quinozine ring group, quinoline ring group, phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline Ring group, carbazole ring group, phenanthridine ring group, acridine ring group, phenanthroline ring group, thianthranyl ring group, benzopyran ring group, xanthene ring group, phenanthiazide ring group base and phenanthroline ring group, phenyl ring group is the best. The aromatic group may connect a plurality of aromatic rings via a single bond or a connecting group described below. As a linking group, an alkylene group is preferable, for example. It is also preferred that the alkylene group is either linear or branched. Specific examples of groups in which a plurality of aromatic rings are connected via single bonds or connecting groups include biphenyl, diphenylmethane, diphenylpropanyl, diphenylisopropyl, and triphenylmethane. base, tetraphenylmethyl, etc.

Examples of the substituent that may have the organic group represented by A ¹ include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; acetyloxy, propyloxy and Benzyloxy and other acyloxy groups; acetyl, benzoyl, isobutyl, acrylic, methacrylyl and methoxyl ethyl groups; methylmercapto and tert-butylmercapto Alkyl mercapto groups; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto groups; alkyl groups such as methyl, ethyl, tert-butyl and dodecyl groups; halogenated alkyl groups such as fluorinated alkyl groups; cyclopentyl, Cycloalkyl groups such as cyclohexyl, cycloheptyl and adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl and phenanthrenyl; hydroxyl; carboxyl; formyl; Sulfo; cyano; alkylaminocarbonyl; arylaminecarbonyl; sulfonamide; silyl; amine; monoalkylamino; dialkylamino; arylamine; diarylamine group; sulfoxy group; or a combination thereof.

L ¹ represents the (m+1) valence linking base. The connecting group is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and an alkylene group (preferably a carbon number of 1 ~10 linear or branched alkenyl group), cycloalkyl group (preferably a cycloalkylene group with 3 to 10 carbon atoms), alkenyl group (preferably a linear or branched alkenyl group with 210 carbon atoms) ) or a connecting base formed by connecting a plurality of them. The total carbon number of the connecting group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group or an alkenylene group, more preferably a linear or branched alkylene group, further preferably a straight chain alkylene group, and particularly preferably an ethyl or methylene group. , methylene is the best.

R ¹ represents a monovalent organic group. Examples of monovalent organic groups include aliphatic groups, aromatic groups, and the like. Examples of the aliphatic group and aromatic group include those described with the above ^A1 . The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those mentioned 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)-valent linking group, and n represents an integer of 1 or more. Examples of the linking group represented by L ² include the groups described with L ¹ above, and the preferable ranges are also the same. Ethylene or methylene is particularly preferred, and methylene is the most preferred. n represents an integer of 1 or more, 1 or 2 is preferred, and 1 is more preferred. The upper limit of n is the maximum number of substituents that can be employed on the linking group represented by ^L2 . If n is 1, a tertiary amine with a high boiling point is likely to be generated by heating at 200°C or lower. Furthermore, the stability of the resin composition can be improved.

m represents an integer above 1, 1 or 2 is preferred, and 1 is more preferred. The upper limit of m is the maximum number of substituents that can be employed in the linking group represented by L ¹ . If m is 1, a tertiary amine with a high boiling point is likely to be generated by heating at 200°C or lower. Furthermore, the stability of the resin composition can be improved. p represents an integer above 1, 1 or 2 is preferred, and 1 is more preferred. The upper limit of p is the maximum number of substituents that can be adopted by the organic group represented by A ¹ . If p is 1, a tertiary amine with a high boiling point is likely to be generated by heating at 200°C or lower.

In the present invention, the compound represented by formula (A1) is preferably a compound represented by the following formula (1a). [Chemical formula 28] In formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m+1)-valent linking group, L ² represents an (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 above 1. 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 preferred ranges are also the same.

In the present invention, the compound represented by formula (A1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in the general formula (A1) 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. N-aryliminodiacetic acid easily produces tertiary amines with high boiling points at temperatures between 120 and 200°C.

Specific examples of the thermal base generator are described below, but the present invention is not limited thereto. These may be used individually or in mixture of two 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) and (A-18) to (A-26) are more preferred, and (A-1) to (A-9) and (A-18 ) to (A-21), (A-23), and (A-24) are further preferred.

[Table 1]

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

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

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

<<Thermal radical polymerization initiator>> The resin composition in the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. Thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, when the cyclization reaction of the polyimide precursor is carried out, the polymerization reaction of the polymerizable compound and the like can proceed. Furthermore, when the polyimide precursor contains a radically polymerizable group, the polymerization reaction of the polyimide precursor can be performed simultaneously with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved. Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, and metallocenes. Compounds, active ester compounds, compounds with carbon-halogen bonds, azo compounds, etc. Among them, peroxides or azo compounds are more preferred, and peroxides are particularly preferred. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90 to 130°C, and more preferably 100 to 120°C. Specific examples include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-63554. 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 mass %, and more preferably 0.1 to 30 mass %. , 0.1 to 20% by mass is particularly preferred. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film with more excellent heat resistance. The number of thermal radical polymerization initiators may be only one type or two or more types. When there are two or more types of thermal radical polymerization initiators, the total amount is preferably within the above range.

＜＜Anti-rust agent>> The resin composition in the present invention preferably contains an anti-rust 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 compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and the compounds described in Japanese Patent Application Laid-Open No. 2011- Compounds described in Paragraph 0052 of Publication No. 59656, compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, etc. Specific examples include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine ring, Compounds containing oxazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds with thioureas and thiol groups, 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 are preferred. , 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-tetrazole are more preferred, and 1H-tetrazole is the best. Examples of commercially available products include KEMITEC BT-C (manufactured by CHEMIPRO KASEI KAISHA, LTD., 1,2,3-benzotriazole), 1HT (manufactured by TOYOBO CO., LTD., 1H-tetrazole), and P5T (TOYOBO CO., LTD., 5-phenyl-tetrazole), etc. In addition, it is also better to use KEMINOX 179 (manufactured by CHEMIPRO KASEI KAISHA, LTD).

When the resin composition contains a rust inhibitor, the content of the rust inhibitor is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass relative to 100 parts by mass of the resin. There may be only one kind of anti-rust agent, or two or more kinds of anti-rust agents. When two or more types are used, the total amount is preferably within the above range.

<<Solvent>> In the present invention, when the resin composition is formed into a layered form by coating, it is preferable to mix a solvent with the resin composition. As the solvent, any known solvent can be used. Examples include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. Examples of the esters preferably include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate, etc.) ), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester, 3-alkoxypropionic acid methyl ester, etc.) -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (e.g., 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy Ethyl-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. Examples of preferred 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 Ester etc. Preferable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like. Preferable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like. Preferable examples of the sericene include dimethyl serotonin.

From the viewpoint of improving the properties of the coating surface, etc., a form in which two or more solvents are mixed is also preferred. Among them, it is 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, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol ethyl A mixed solution composed of two or more of acid ester, propylene glycol methyl ether and propylene glycol methyl ether acetate is preferred. It is particularly suitable to use dimethylsulfoxide and γ-butyrolactone at the same time.

When the resin composition contains a solvent, from the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid concentration of the resin composition becomes 5 to 80 mass %, and further preferably 5 to 70 mass %. Best, 10-60% by mass is particularly good. The solvent content can be adjusted by the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent is preferably such that the solid content concentration falls within the above range. In the case of the spray coating method, the amount is preferably 0.1 mass% to 50 mass%, and the amount is more preferably 1.0 mass% to 25 mass%. By adjusting the amount of solvent by the coating method, a resin composition layer of a desired thickness can be formed uniformly. There may be only one type of solvent, or two or more types of solvents may be used. When there are two or more solvents, the total amount is preferably within the above range. Furthermore, from the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylmethane The content of amide is preferably less than 5% by mass relative to the total mass of the resin composition, more preferably less than 1% by mass, still more preferably less than 0.5% by mass, and still more preferably less than 0.1% by mass.

<< Sensitizing dye >> The resin composition in the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and enters an electronically excited state. The sensitizing dye that becomes an electronically excited state comes into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc. to produce electron transfer, energy transfer, heat generation and other effects. Thereby, the thermal base generator, the photobase generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo chemical changes and decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification. When the resin composition contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and further 0.5 to 10 mass %. Better. One type of sensitizing dye may be used alone, or two or more types of sensitizing dyes may be used simultaneously.

<<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 Polymer Dictionary, 3rd Edition (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 the molecule is used. These donate hydrogen to low-activity radical species to generate free radicals, or can generate free radicals by deprotonating them after being oxidized. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole) 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 further preferably 100 parts by mass of the total solid content of the resin composition. 1 to 5 parts by mass. There may be only one type of chain transfer agent, or two or more types of chain transfer agents may be used. When there are two or more chain transfer agents, the total amount is preferably within the above range.

<<Surfactant>> From the viewpoint of improving coatability, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred. [Chemical formula 29]

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 mass%, more preferably 0.005 to 1.0 mass%. There may be only one type of surfactant, or two or more types of surfactants may be used. When two or more surfactants are contained, the total amount is preferably within the above range.

<<Higher fatty acid derivatives>> In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention after coating. It exists locally on the surface of the composition during the drying process. When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or two or more types of higher fatty acid derivatives may be used. When there are two or more types of higher fatty acid derivatives, the total amount is preferably within the above range.

<<Other additives>> Within the scope that does not impair the effects of the present invention, the resin composition of the present invention can be blended with various additives as needed, such as inorganic particles, hardeners, hardening catalysts, fillers, and antioxidants. , UV absorbers, anti-aggregation agents, etc. When these additives are blended, the total blending 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 coating surface, the moisture content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and less than 0.6 Quality % 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), further preferably less than 1 mass ppm, and less than 0.5 mass ppm. Excellent. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total amount of these metals is preferably within the above range. In addition, as a method of reducing metal impurities unintentionally contained in the resin composition, a raw material containing a small metal content is selected as a raw material constituting the resin composition, and the raw material constituting the composition of the present invention is filtered with a filter. Methods such as lining the device with polytetrafluoroethylene and performing distillation under conditions that suppress contamination as much as possible.

From the viewpoint of wiring corrosion, the content of halogen atoms in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, the amount of halogen ions present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total number of chlorine atoms and bromine atoms or chloride ions and bromide ions is within the above range.

<Preparation of Resin Composition> The resin composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by conventionally known methods. In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as garbage and particles in the resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be pre-cleaned with organic solvents. In the filtration process of the filter, multiple types of filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. Alternatively, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, impurity removal using adsorbent materials can also be performed. It is also possible to combine filter filtration and impurity removal using adsorbent materials. As the adsorbent material, known adsorbent materials can be used. Examples include inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon.

<Manufacturing method of laminated body> Next, the manufacturing method of the laminated body of this invention is demonstrated. The manufacturing method of the laminated body of this invention includes the manufacturing method of the film of this invention mentioned above. That is, the manufacturing method of the laminated body of this invention includes the process of manufacturing a film using the above-mentioned manufacturing method of the film of this invention.

In the manufacturing method of the laminated body of this invention, it is preferable to repeat the process of manufacturing a film using the above-mentioned manufacturing method of the film of this invention two or more times.

Moreover, it is preferable that the manufacturing method of the laminated body of this invention further includes the process of forming a metal layer. Specifically, it is preferable to form a metal layer on the film produced by the film production method of the present invention. The metal layer is not particularly limited, and existing metal types 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 of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. Examples include photolithography, lift-off, electroplating, electroless plating, etching, printing, and methods combining them; patterning methods that combine sputtering, photolithography, and etching; and methods that combine photolithography and etching. Patterning method by electrolytic plating is preferred. As for the thickness of the metal layer, the thickest part is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

When the manufacturing method of the laminated body of the present invention includes a process of forming a metal layer, it may also include a surface activation treatment process of surface-activating at least part of the metal layer and the resin composition layer. The surface activation treatment may be performed only on at least a part of the metal layer, or may be performed only on at least a part of the resin composition layer after the heating process, or it may be performed on both the metal layer and the resin composition layer after the heating process. at least part of the process.

The surface activation treatment can be performed after the metal layer is formed, or the metal layer can be formed after the heating process and the surface activation treatment on the resin composition layer. Regarding the surface activation treatment, it is preferable to perform surface activation treatment on at least a part of the metal layer, and it is preferable to perform surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed on the surface. By performing surface activation treatment on the surface of the metal layer, the adhesion of the resin composition layer provided on the surface can be improved. In addition, surface activation treatment may be preferably performed on part or all of the resin composition layer after the heating process. In this way, by surface-activating the surface of the resin composition layer, the adhesion to the metal layer or the resin composition layer provided on the surface that has been surface-activated can be improved.

As the surface activation treatment, plasma treatment, corona discharge treatment, CF ₄ /O ₂ -based treatment with various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) Etching treatment of NF ₃ /O ₂ , SF ₆ , NF ₃ and NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then removing the oxide film containing amine groups and thiols Impregnation treatment with an organic surface treatment agent containing at least one compound in the base, mechanical roughening treatment using a brush, and plasma treatment are preferred, and oxygen plasma treatment using oxygen for the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500~200000J/ ^m2 , 1000~100000J/ ^m2 is better, and 10000~50000J/ ^m2 is optimal.

In the manufacturing method of the laminated body of the present invention, the process of manufacturing a film by the film manufacturing method of the present invention and the process of forming a metal layer on the obtained film are preferably carried out alternately two or more times, and more preferably 2 to 7 times. , it is more preferable to carry out 2 to 5 times. Thereby, it is possible to produce a laminated body of a plurality of layers of wiring structures in which a plurality of resin layers and metal layers composed of resin composition layers are alternately laminated. In addition, as the number of laminated layers increases, 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. However, according to the manufacturing method of the laminated body of the present invention, even if the number of laminated layers is increased, There will be no peeling between the layers.

FIG. 1 is a diagram showing an example of a laminate having a plurality of layers of wiring structure. Symbol 500 in the figure represents a laminated body, symbols 201 to 204 represent resin layers, and symbols 301 to 303 represent metal layers. A desired pattern is formed in the resin layer 201 . For example, the pattern can be formed by negative development. A metal layer 301 is formed on the surface of the resin layer 201 . The metal layer 301 is formed to cover 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 in the resin layer 202 . A metal layer 302 is formed on the surface of the resin layer 202 . The metal layer 302 is formed 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 in 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 in the resin layer 203 . A metal layer 303 is formed on the surface of the resin layer 203 . The metal layer 303 is formed to cover part of the surface of the groove 403 formed in the resin layer 203 and is electrically connected to the metal layer 302 exposed in 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 in the resin layer 204 . In addition, in FIG. 1 , a part of the metal layer 302 is also exposed in the resin layer 204 . This laminated body functions as an insulating film for the resin layers 201 to 204, and the metal layers 301 to 303 function as wiring layers. This kind of laminate can be suitably used as a rewiring layer in electronic components.

<Manufacturing method of electronic component> Next, one embodiment of an electronic component obtained by applying the film manufacturing method of the present invention will be described. The electronic component 100 shown in FIG. 2 is a so-called three-dimensional mounting component, and a laminate 101 in which a plurality of semiconductor components (semiconductor wafers) 101 a to 101 d are laminated is arranged on a wiring substrate 120 . In addition, in this embodiment, the description is mainly based on the case where the number of laminated semiconductor elements (semiconductor wafers) is four layers. However, the number of laminated semiconductor elements (semiconductor wafers) is not particularly limited. For example, the number of laminated semiconductor elements (semiconductor wafers) may be two layers, eight layers, or 16th floor, 32nd floor, etc. Also, it can be 1 layer.

The plurality of semiconductor elements 101a to 101d each include 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. The semiconductor elements 101b to 101d have through-electrodes 102b to 102d, and connection pads (not shown) integrally provided with the through-electrodes are provided on both sides of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a without through-electrodes and semiconductor elements 101b to 101d having through-electrodes 102b to 102d are flip-chip bonded. That is, the electrode pad of the semiconductor element 101a that does not have a through-electrode and the connection pad on the semiconductor element 101a side of the adjacent semiconductor element 101b that has the through-electrode 102b are connected by a metal bump 103a such as a solder bump. Furthermore, 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 adjacent semiconductor element 101c having the through-electrode 102c are connected by metal bumps 103b such as solder bumps. connection. Similarly, the connection pad on the other side of the semiconductor element 101c having the through-electrode 102c and the connection pad on the semiconductor element 101c side of the adjacent semiconductor element 101d having the through-electrode 102d are connected by metal bumps such as solder bumps. 103c while connected.

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

The laminate 101 is laminated on the wiring board 120 . As the wiring board 120, for example, a multi-layer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 using a resin substrate include a multi-layer copper-clad laminate (multi-layer printed wiring board).

Surface electrode 120a is provided on one side of wiring substrate 120. The insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring board 120 and the laminated body 101. The wiring board 120 and the laminated body 101 are electrically connected via the rewiring layer 105. The insulating layer 115 is formed using the manufacturing method of the laminated body of the present invention. The insulating layer 115 may have a multi-layer wiring structure as shown in FIG. 1 . One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. Furthermore, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Furthermore, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120. [Example]

Hereinafter, the present invention will be further described in detail through examples. However, the present invention is not limited to the following examples within the scope that does not deviate from the gist of the invention. In addition, unless otherwise specified, "%" and "parts" are based on mass. NMR is the abbreviation of 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 groups Synthesis of imine precursor)] Suspend 14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58 mmol) of benzyl alcohol in 50 ml of N-methylpyrrolidone and dried through molecular sieves. The suspension was heated at 100°C for 3 hours. Heating was started and a clear solution was obtained after a few minutes. 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 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10±4°C. 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, 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at 20 to 23°C. The solution obtained. Then, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was filtered, poured into 4 liters of water again, stirred for 30 minutes, and filtered again. Next, 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 30]

(Synthesis Example 2) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (P-2: having free radicals Synthesis of polyimide precursor of polymerizable group] 14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 mmol) of 2-Hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine and 140g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed, and at a temperature of 60°C The mixture was stirred for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated with SOCl ₂ , 4,4'-diaminodiphenyl ether was used to convert into a polyimide precursor in the same manner as in Synthesis Example 1, and the same method as in Synthesis Example 1 was used. 1 A polyimide precursor (P-2) containing a repeating unit represented by the following formula was obtained in the same manner. [Chemical formula 31]

(Synthesis Example 3) [Polyimide precursor (P derived from 4,4'-oxybisphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate) -3: Synthesis of polyimide precursor with radical polymerizable groups] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride (dried at 140°C for 12 hours), 18.6g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine and 140g of diethylene glycol dimethyl ether were mixed, and at 60°C The mixture was stirred for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated with SOCl ₂ , 4,4'-diaminodiphenyl ether was used to convert into a polyimide precursor in the same manner as in Synthesis Example 1, and the same method as in Synthesis Example 1 was used. 1 A polyimide precursor (P-3) containing a repeating unit represented by the following formula was obtained in the same manner. [Chemical formula 32]

(Synthesis Example 4) [Synthesis of Acrylic Polymer (P-4)] 27.0 g (153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropylmethacrylate Amide, 39 g (309.2 mmol) allyl methacrylate, 13 g (151.0 mmol) methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 mmol) and 300g of 3-methoxy-2-propanol were mixed. In a nitrogen atmosphere, the mixed liquid 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 in a nitrogen atmosphere. After the reaction was completed, 5 liters of water was added to precipitate the polymer, and the mixture was stirred at a speed of 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, poured into 4 liters of water again, and further stirred for 30 minutes, and filtered and removed again. Next, the obtained acrylic resin was dried at 45° C. for 3 days under reduced pressure to obtain an acrylic polymer (P-4) represented by the following formula. [Chemical formula 33]

<Preparation of Photosensitive Resin Composition> The components described below were mixed to prepare a coating liquid of a photosensitive resin composition as a uniform solution. (Composition) Resin: The mass parts of the radically polymerizable compound described in the following table: The mass parts of the photoradical polymerization initiator described in the following table: The mass parts of the silane coupling agent described in the following table: Parts by mass of the rust inhibitor described in the following table: Parts by mass of the polymerization inhibitor described in the following table: Parts by mass of the base generator described in the following table: Parts by mass of solvent 1 described in the following table (Dimethylstyrene): 100 parts by mass Solvent 2 (γ-butyrolactone): 25 parts by mass

[Table 6]

The abbreviations recorded 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-4: Acrylic synthesized in Synthesis Example 4. Polymer (P-4)

(Radically polymerizable compound) B-1: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co, Ltd., ethoxylated isocyanurate triacrylate) B-2: SR209 (manufactured by Sartomer company Inc. , tetraethylene glycol diacrylate)

(Photoradical polymerization initiator) C-1: IRGACURE OXE 01 (manufactured by BASF, oxime compound) C-2: ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION, oxime compound)

(Silane coupling agent) D-1: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, with Silane coupling agent with amine group) D-2: Triethoxysilylpropylmaleamide (manufactured by Gelest, Inc., silane coupling agent with carboxyl group) D-3: KBE-502 (Shin-Etsu Chemical Co., Ltd., 3-methacrylmethyldiethoxysilane, silane coupling agent with methacrylic acid group) D-4: SILQUEST A-137 (Momentive Performance Materials Inc., non-reactive Silane coupling agent with reactive group) D-5: SILQUEST A-LINK599 (silane coupling agent without reactive group, manufactured by Momentive Performance Materials Inc.) D-6: KBM-403 (Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidyl ether propyltrimethoxysilane, silane coupling agent with epoxy group) D-7: KBE-803 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyltrimethoxysilane) Silane, silane coupling agent with mercapto group)

(Rust inhibitor) E-1: KEMITEC BT-C (manufactured by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole) E-2: KEMINOX 179 (manufactured by CHEMIPRO KASEI KAISHA, LTD) E-3: 1HT (manufactured by TOYOBO CO., LTD., 1H-tetrazole)

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

(Base generator) A-21, A-40: Compounds with the following structure (thermal base generator) A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photobase generator) [Chemical Formula 34]

<Manufacture of laminated body> The laminated body shown in FIG. 3 was produced. In FIG. 3 , symbol 1010 is a silicon wafer, symbol 1020 is a resin layer, and symbol 1030 is a metal layer. The silicon wafer 1010 has a diagonal line drawn toward the lower left side, the resin layer 1020 is a hollow layer, and the metal layer 1030 has a diagonal line drawn toward the lower right side.

Each resin composition was pressure-filtered through a filter with a pore width of 0.8 μm, and then applied in a layer by spin coating on a silicon wafer 1010 having a metal layer 1030 using a heating plate. It was dried at 100° C. for 5 minutes to form a resin composition layer. Next, the resin composition layer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm ² . Next, development was performed for 60 seconds using cyclopentanone to remove the resin composition layer in the unexposed portion, thereby forming holes with a diameter of 10 μm. Next, a heating process was performed in a nitrogen environment under the conditions described in the following table, and then cooled to room temperature to form the resin layer 1020 . Next, the resin layer 1020 was subjected to a copper plating process, and a copper thin film (metal layer 1030 ) with a thickness of 5 μm was formed on the resin layer 1020 to form the laminated body 1 . Next, after irradiating the copper thin film (metal layer 1030) of the laminated body 1 with oxygen plasma, the resin composition is again applied, exposed, developed, and heated under the conditions described in the table below to form the resin layer 1020. Thus, the laminated body 2 was obtained. Next, copper plating is performed on the resin layer 1020 of the laminated body 2 to form a copper thin film (metal layer 1030). Next, after the copper thin film (metal layer 1030) on the laminated body 2 is irradiated with oxygen plasma, the resin composition is applied, exposed, developed, and heated under the same conditions as the formation of the laminated body 1 to form the resin layer 1020. Thus, the laminated body 3 was obtained. Next, copper plating is performed on the resin layer 1020 of the laminated body 3 to form a copper thin film (metal layer 1030). Next, after the copper thin film (metal layer 1030) on the laminated body 3 is irradiated with oxygen plasma, the resin composition is applied, exposed, developed, and heated under the same conditions as the formation of the laminated body 1 to form the resin layer 1020. Thus, the laminated body 4 (the laminated body shown in FIG. 3) was obtained.

(Heating conditions) Condition 1: Heating at 130° C. for 40 minutes (first-stage heating), and then heating at 200° C. for 300 minutes (second-stage heating). Condition 2: Heating at 150°C for 30 minutes (first-stage heating), and then heating at 230°C for 180 minutes (second-stage heating). Condition 3: Heating at 170°C for 10 minutes (first-stage heating), followed by heating at 250°C for 120 minutes (second-stage heating). Condition 4: Heating at 200°C for 340 minutes. Condition 5: Heating at 230°C for 210 minutes. Condition 6: Heating at 250°C for 130 minutes. Conditions 1 to 3 are two-stage heating, and conditions 4 to 6 are one-stage heating.

<Evaluation> The laminate 4 obtained above was subjected to a thermal cycle test in accordance with JEDEC JESD22-A104B (3 hours at -55°C/125°C was set as one cycle, a total of 1000 cycles), and then a scanning electron microscope was used. The cross-sections were observed with an optical microscope. The interface between the silicon wafer 1010 and the resin layer 1020, the interface between the resin layer 1020 and the metal layer 1030, and the interface between the resin layers 1020 were checked for peeling, and the adhesion was evaluated based on the following criteria. Here, as shown in FIG. 4 , when a gap S is found between the metal layer 1030 and the resin layer 1020 , it is determined that peeling is found at the interface between the resin layer 1020 and the metal layer 1030 . Other interfaces are also judged based on the same criteria. A: There is no peeling in any of the interface between the silicon wafer 1010 and the resin layer 1020, the interface between the resin layer 1020 and the metal layer 1030, and the interface between the resin layers 1020. B: There is no peeling in any of the interfaces between the silicon wafer 1010 and the resin layer 1020, the interface between the resin layer 1020 and the metal layer 1030, and the interfaces between the resin layers 1020, but it is found in any of them. It seems that the part needs to be stripped off. Specifically, no voids caused by obvious peeling were observed at the interface (dark when observed with a microscope), but some gray-white parts in the interface were observed like shadows. C: Peeling is observed in any one of the interface between the silicon wafer 1010 and the resin layer 1020 , the interface between the resin layer 1020 and the metal layer 1030 , and the interface between the resin layers 1020 .

[Table 7]

As shown in the above table, in the Examples, a laminated body excellent in adhesiveness can be produced.

1～4‧‧‧Laminated body 100‧‧‧Electronic component 101a～101d‧‧‧Semiconductor element 101‧‧‧Laminated body 102b～102d‧‧‧Through electrodes 103a～103e‧‧‧Metal bump 105‧‧‧Re Wiring layers 110, 110a, 110b‧‧‧Underfill layer 115‧‧‧Insulating layer 120‧‧‧Wiring substrate 120a‧‧‧Surface electrodes 201～204‧‧‧Resin layers 301～303‧‧‧Metal layers 401～403 ‧‧‧Trough 500‧‧‧Laminated body 1010‧‧‧Silicon wafer 1020‧‧‧Resin layer 1030‧‧‧Metal layer S‧‧‧Gap

FIG. 1 is a schematic diagram showing the structure of an embodiment of the laminate. FIG. 2 is a schematic diagram showing the structure of an embodiment of an electronic component. FIG. 3 is a schematic diagram of the laminated body produced in the Example. FIG. 4 is a schematic diagram showing the peeling state of the resin layer and the metal layer.

201~204‧‧‧Resin layer

301~303‧‧‧Metal layer

401~403‧‧‧Slot

500‧‧‧Laminated body

Claims (14)

A method for manufacturing a film, which uses a resin composition containing a polyimide precursor and a silane coupling agent having a reactive group to form a resin composition layer on a support, where the resin composition is a photosensitive resin composition, After the resin composition layer is exposed and developed to form a pattern, the resin composition layer is heated in two or more stages, and the second stage is performed at a temperature higher than the heating temperature in the first stage. Heat. As for the film manufacturing method described in item 1 of the patent application, the heating in the first stage is performed at a temperature of 130 to 170°C for 10 to 60 minutes. For example, in the method for manufacturing a film described in Item 1 or Item 2 of the patent application, the heating in the first stage is carried out at a temperature of 130 to 170°C for 20 to 60 minutes. For example, the manufacturing method of the film described in item 1 or 2 of the patent application scope, wherein the aforementioned second stage heating is performed at a temperature of 180~250°C for 60~300 minutes. The method for manufacturing a film as described in item 1 or 2 of the patent application, wherein the reactive group of the silane coupling agent is selected from the group consisting of acid groups, amine groups, groups with ethylenically unsaturated bonds, and rings. At least one of the ether groups. The method for manufacturing a film as described in item 1 or 2 of the patent application, wherein the reactive group of the silane coupling agent is selected from the group consisting of acid groups, groups with ethylenically unsaturated bonds, and cyclic ether groups. At least one of them. The method for manufacturing a film as described in item 1 or 2 of the patent application, wherein the aforementioned polyimide precursor is a polyimide precursor containing a repeating unit represented by 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 1-valent organic base. The method for manufacturing a film according to claim 1 or 2, wherein the resin composition layer is formed by coating the resin composition on a support. A method for manufacturing a laminated body, which includes the method for manufacturing a film as described in any one of items 1 to 8 of the patent application. The manufacturing method of a laminated body according to claim 9, wherein the process of manufacturing a film using the film manufacturing method described in any one of claims 1 to 8 is repeated two or more times. The method for manufacturing a laminated body as described in Item 9 or Item 10 of the patent application further includes a process of forming a metal layer. The method for manufacturing a laminated body as described in Item 9 of the patent application, wherein a process for manufacturing a film using the film manufacturing method as described in any one of Items 1 to 8 of the Application and on the aforementioned film The process of forming the metal layer is performed alternately for more than two times. A method for manufacturing electronic components, which includes the method for manufacturing a film as described in any one of items 1 to 8 of the patent application scope. A method of manufacturing an electronic component, which includes the method of manufacturing a laminated body as described in any one of items 9 to 12 of the patent application.