TWI736629B - Manufacturing method of laminated body and manufacturing method of semiconductor element - Google Patents

Abstract

A method for manufacturing a laminate includes the following processes in sequence: a photosensitive resin composition layer forming process, applying the photosensitive resin composition to a substrate to form a layer; an exposure process corresponding to the photosensitive resin composition used in the substrate The resin composition layer is exposed; the development process is to develop the exposed photosensitive resin composition layer; the curing process is to harden the developed photosensitive resin composition layer; and the metal layer formation process is used by air The phase film is formed on the surface of the photosensitive resin composition layer after the curing process to form a metal layer. The temperature of the photosensitive resin composition layer after the curing process when the metal layer is formed is lower than that of the photosensitive resin composition layer after the curing process. Glass transition temperature.

Description

Manufacturing method of laminated body and manufacturing method of semiconductor element

The present invention relates to a method for manufacturing a laminate, a method for manufacturing a semiconductor element, and a laminate.

Resins such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation properties, and therefore are used in insulating layers of semiconductor elements and the like.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: International Publication No. WO2011/034092

As the interlayer insulation film for the rewiring layer of the semiconductor element, a cured film of a resin excellent in heat resistance and insulation such as polyimide resin or polybenzoxazole resin is used, and the cured film and metal are laminated Layer to manufacture the rewiring layer of the semiconductor element.

The inventors of the present invention conducted research on the cured film and metal layer of a resin with excellent heat resistance and insulation such as polyimide resin or polybenzoxazole resin, and found that the adhesion between the cured film and the metal layer It is not sufficient, and interlayer peeling occurs between the cured film and the metal layer.

Here, in the film forming method used in the manufacture of semiconductor elements, a barrier metal film is usually provided between the substrate and the wiring layer including copper (Cu), etc., thereby preventing the material constituting the wiring layer from diffusing on the substrate. Deterioration of the wiring caused by it (see Patent Document 1).

Patent Document 1 describes a method for forming a barrier metal film, in which a substrate with fine holes or grooves formed on the surface is prepared, and the temperature of the substrate is set in the range of 150°C or higher and 500°C or lower on the substrate. A barrier metal film including titanium or titanium compound is formed. According to Patent Document 1, it is described that by using the barrier metal film formation method of the above-mentioned structure, it is possible to reduce the occurrence of sag in the opening (the diameter of the opening becomes larger than the bottom Small case). However, in Patent Document 1, attention is only paid to the case where a silicon oxide film is formed on the surface of a silicon wafer as a substrate. That is, in Patent Document 1, only attention has been paid to interlaminar peeling when a cured film and a metal layer are laminated with a resin excellent in heat resistance and insulation, such as polyimide resin or polybenzoxazole resin.

The problem to be solved by the present invention is to provide a method of manufacturing a laminate that can suppress delamination when a substrate, a cured film, and a metal layer are laminated. In addition, the problem to be solved by the present invention is to provide a method of manufacturing a semiconductor element including a method of manufacturing a laminate. In addition, the problem to be solved by the present invention is to provide a laminate that can suppress delamination when a substrate, a cured film, and a metal layer are laminated.

As a result of the inventors’ research on the above-mentioned problems, they found that the sputtering method is used at a temperature lower than the glass transition temperature of a cured film of a resin excellent in heat resistance and insulation, such as polyimide resin or polybenzoxazole resin. The above-mentioned problems can be solved by forming a metal layer by forming a film in a vapor phase. The present invention as a method for solving the above-mentioned problems and preferred aspects of the present invention are as follows. [1] A method of manufacturing a laminate, which includes the following processes in sequence: a photosensitive resin composition layer forming process, applying the photosensitive resin composition to a substrate to form a layer; an exposure process corresponding to the substrate The photosensitive resin composition layer is exposed; the development process is to develop the exposed photosensitive resin composition layer; the curing process is to harden the developed photosensitive resin composition layer; and the metal layer formation process, A metal layer is formed on the surface of the photosensitive resin composition layer after the curing process by vapor phase film formation; and the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is lower than the photosensitive resin composition layer after the curing process The glass transition temperature of the resin composition layer. [2] The method of manufacturing a laminate as described in [1], which further includes a photosensitive resin composition layer forming process, an exposure process, a development process, a hardening process, and a metal layer forming process that are performed in sequence again. [3] In the method for producing a laminate as described in [1] or [2], the photosensitive resin composition constructs a cross-linked structure by exposure to light, and its solubility in an organic solvent is reduced. [4] The method for producing a laminate according to any one of [1] to [3], wherein the photosensitive resin composition includes a precursor selected from the group consisting of a polyimide precursor, a polyimide, and a polybenzoxazole precursor At least one of resin and polybenzoxazole. [5] The method of manufacturing a laminate according to any one of [1] to [4], further comprising a second metal layer forming process for forming a second metal layer on the surface of the metal layer. [6] The method of manufacturing a laminate as described in [5], wherein the second metal layer includes copper. [7] The method for producing a laminate according to any one of [1] to [6], wherein the metal layer contains at least one of the following compounds, and the compound contains at least one of titanium, tantalum, and copper. [8] The method for producing a laminate according to any one of [1] to [7], wherein the thickness of the metal layer formed in the metal layer forming process is 50 to 2000 nm. [9] In the method for manufacturing a laminate as described in any one of [1] to [8], the residual stress of the photosensitive resin composition after the curing process measured in accordance with the laser measurement method is less than 35 MPa. [10] The method for producing a laminate according to any one of [1] to [9], wherein the photosensitive resin composition is a photosensitive resin composition for negative development. [11] The method for manufacturing a laminate as described in any one of [1] to [10], wherein the curing process includes a temperature-rising process of raising the temperature of the photosensitive resin composition layer and a temperature equal to the final temperature of the temperature-rising process. The holding temperature is maintained during the holding process, and the holding temperature in the process is kept below 250°C. [12] The method for producing a laminate according to any one of [1] to [11], wherein the temperature of the photosensitive resin composition layer when the metal layer is formed is lower than the glass transition temperature of the photosensitive resin composition layer Above 30°C. [13] A method of manufacturing a semiconductor element, comprising the method of manufacturing a laminate according to any one of [1] to [12]. [14] A laminate having a substrate, a patterned hardened film, and a metal layer on the surface of the aforementioned patterned hardened film, the patterned hardened film includes polyimide or polybenzoxazole, and forms the metal on the surface of the patterned hardened film The penetration length of the metal of the layer into the patterned cured film is 130 nm or less from the surface of the patterned cured film.

[15] A laminate produced by the method for producing a laminate according to any one of [1] to [12]. [16] A semiconductor device manufactured by the method of manufacturing a semiconductor device described in [13]. [Effects of the invention]

According to the present invention, it is possible to provide a method of manufacturing a laminate that can suppress delamination when a substrate, a cured film, and a metal layer are laminated. Furthermore, according to the present invention, it is possible to provide a method of manufacturing a semiconductor element including the method of manufacturing a laminate of the present invention. Furthermore, according to the present invention, it is possible to provide a laminate that can suppress delamination when the substrate, the cured film, and the metal layer are laminated. [Illustration brief description]

FIG. 1 is a schematic diagram showing the structure of an embodiment of a semiconductor element. Fig. 2 is a schematic diagram showing the structure of an embodiment of a laminate obtained by the method of manufacturing a laminate of the present invention.

The description of the constituent elements in the present invention described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. Regarding the label of the group (atomic group) in this specification, the label that does not record substituted and unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, active rays or radiations such as extreme ultraviolet, extreme ultraviolet (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers are usually cited. In this specification, the numerical range indicated by "～" refers to the range that includes the numerical values described before and after "～" as the lower limit and the upper limit. In this manual, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "methyl "Allyl" means both or either, "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", "(meth)acrylic acid" means "acrylic acid" And either or both of "methacryloyl". In this manual, the term "process" is not only an independent process, but even if it can be clearly distinguished from other processes, if the desired effect of the process can be achieved, it is also included in this term. In this specification, the solid content concentration is the mass percentage of components other than the solvent in the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined based on the styrene conversion value of gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent is measured with THF (tetrahydrofuran). In addition, as long as there is no special description, the detection is to use a UV ray (ultraviolet) wavelength 254 nm detector.

The manufacturing method of the laminated body of the present invention includes the following processes in sequence: a photosensitive resin composition layer forming process, applying the photosensitive resin composition to a substrate to form a layer; an exposure process corresponding to the photosensitive for the substrate The resin composition layer is exposed; the development process is to develop the exposed photosensitive resin composition layer; the curing process is to harden the developed photosensitive resin composition layer; and the metal layer formation process is used by air A metal layer is formed on the surface of the photosensitive resin composition layer after the curing process, and the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is lower than that of the photosensitive resin composition layer after the curing process The glass transition temperature. With the above structure, it is possible to suppress delamination when the substrate, the cured film, and the metal layer are laminated. When a metal layer is formed on the surface of the cured film (the cured film refers to the photosensitive resin composition layer after the curing process) formed on the substrate by a vapor phase such as sputtering method, the substrate is usually controlled in order to control the film quality of the metal layer. (And hardened film) to heat. Conventionally, if a metal layer is formed using a sputtering method at a relatively high temperature, metal atoms can be driven into the cured film. As a result, it is estimated that the generation of delamination can be suppressed. In fact, the inventors of the present invention analyzed the cross section of a laminate with a metal layer formed on the surface of the cured film using a sputtering method using a transmission electron microscope (Transmission Electron Microscope; TEM), etc., and found that Sputtering is used to form a metal layer at a temperature of 90°C, and penetration of the metal into the surface of the hardened film occurs. However, it is known that if the metal layer is formed by using the sputtering method at a relatively high temperature, delamination occurs when the substrate, the cured film, and the metal layer are laminated. On the other hand, it is known that the temperature of the photosensitive resin composition layer after the curing process (the temperature of the surface of the cured film) is suppressed to be lower than the glass transition temperature by vapor phase film formation such as sputtering. When the metal layer is formed, there is no penetration of the metal into the surface of the hardened film, and no delamination occurs when the substrate, hardened film, and metal layer are laminated. Hereinafter, the glass transition temperature is referred to as Tg (glass transition temperature). Hereinafter, the preferred aspects of the present invention will be described in detail.

<Filtration Process> The method of manufacturing the laminate of the present invention may include a process of filtering the photosensitive resin composition before applying the photosensitive resin composition to the substrate. It is better to use filters for filtering. The aperture of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter can be cleaned in advance with an organic solvent. In the filter filtering process, multiple filters can be used in series or in parallel. When multiple filters are used, filters with different apertures and/or materials can be used in combination. In addition, various materials can be used to perform multiple filtrations, and the process for performing multiple filtrations may be a cyclic filtration process. In addition, pressure filtration can be performed, and the pressure applied during pressure filtration is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtering with a filter, an adsorbent can also be used for filtering to remove impurities, or a combination of filter filtering and adsorbent can be used for filtering. As the adsorbent, well-known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<<Photosensitive resin composition layer formation process>> The manufacturing method of the laminate of the present invention includes a photosensitive resin composition layer formation process in which a photosensitive resin composition is applied to a substrate to form a layer. As a method to be applied to the substrate, coating is preferred. Specifically, as the application method, there can be exemplified dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the application method, the desired photosensitive resin composition layer can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method Or spraying method, inkjet method, etc. are preferable. When using the spin coating method, for example, it can be applied at 500 to 2000 rpm (revolutions per minute) for about 10 seconds to 1 minute. Regarding the thickness of the photosensitive resin composition layer (cured film after the curing process) After the exposure, it is preferable to apply the coating so that it becomes 0.1-100μm, and it is more preferable to apply the coating so that it becomes 1-50μm. Also, as shown in Figure 2, the formed photosensitive resin composition layer The thickness does not need to be uniform. In particular, when the photosensitive resin composition layer is provided on the uneven surface, as shown in Figure 2, cured films with different thicknesses should be obtained. Especially when multiple layers of the cured film are laminated, the recesses are also Deep recesses can be formed, but compared with this structure, the present invention has a higher technical value in that it can more effectively inhibit delamination between layers. When the laminate has cured films with different thicknesses, the thinnest part of the cured film The thickness of is preferably the above-mentioned thickness.

＜＜Substrate＞＞ The type of substrate can be appropriately set according to the application, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon and other semiconductor manufacturing substrates, quartz, glass, optical films, ceramic materials, vapor-deposited films, Magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc. There are no special restrictions. In the present invention, a substrate for semiconductor manufacturing is particularly preferable, and silicon is more preferable. In addition, when the photosensitive resin composition layer is formed on the surface of the cured film or the surface of the metal layer, the cured film or the metal layer can be used as a substrate.

<<Photosensitive resin composition>> Hereinafter, the photosensitive resin composition used in the present invention will be described in detail. In the manufacturing method of the laminate of the present invention, the photosensitive resin composition preferably contains a compound that forms a cross-linked structure by exposure, and it is more preferable for negative-type development. The cross-linked structure is constructed by exposure to reduce the resistance The solubility of organic solvents is particularly good, and negative photosensitive resins developed with organic solvents are the best. First, the components that can be contained in the photosensitive resin composition used in the present invention will be described. The photosensitive resin composition may contain components other than these, but these components are not essential components.

<<<Resin>>> The photosensitive resin composition used in the present invention contains a resin. In the photosensitive resin composition used in the present invention, the resin is not particularly limited, and a known resin can be used. The resin is preferably a resin with high heat resistance.

The photosensitive resin composition used in the present invention preferably contains at least one resin selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole. In the manufacturing method of the laminated body of this invention, it is more preferable that the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor, and it is more preferable that it contains a polyimide precursor.

The photosensitive resin composition used in the present invention may contain only one selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole, or two above. In addition, two or more polyimide precursors may be included, that is, two or more resins of the same type and different structures may be included. The content of the resin in the photosensitive resin composition used in the present invention is preferably 10 to 99% by mass of the total solid content of the photosensitive resin composition, more preferably 50 to 98% by mass, and 70 to 96% by mass To be further preferred.

Furthermore, it is preferable that the resin contains a polymerizable group. Moreover, it is preferable that the photosensitive resin composition contains a polymerizable compound. With this structure, a three-dimensional network is formed in the exposed area to become a strong crosslinked film. The photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and is cured by the surface activation treatment. The adhesion between the film and the metal layer or the adhesion between the cured films is more effectively improved. In addition, the resin preferably contains a partial structure represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and Including a combination of two or more of the above groups. With this structure, the photosensitive resin composition layer (cured film) becomes a flexible structure, and the effect of suppressing delamination between layers is more effectively exerted. Ar is preferably a phenylene group, L is an aliphatic hydrocarbon group with 1 or 2 carbons which may be substituted by a fluorine atom, and -O-, -CO-, -S- or -SO ₂ -is more preferred. Among them, the aliphatic hydrocarbon group is preferably an alkylene group.

式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基，R¹¹⁵ 表示4價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。(Polyimine Precursor) The type of polyimide precursor is not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1]

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

^{A 1} and A ² in the formula (2) are preferably an oxygen atom or NH, more preferably an oxygen atom. ^{R 111} in the formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, linear or branched aliphatic groups with 2 to 20 carbons, and rings with 6 to 20 carbons. A morphological aliphatic group, an aromatic group having 6 to 20 carbon atoms, or a group including a combination thereof are preferred, and a group including an aromatic group having 6 to 20 carbon atoms is more preferred. ^{As a particularly preferred embodiment, R 111} in the formula (2) can be exemplified as a group represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and Including a combination of two or more of the above groups. These preferable ranges are the same as described above.

^{Preferably, R 111} in formula (2) is derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it is one of a group containing a linear or branched aliphatic group having 2 to 20 carbons, a cyclic aliphatic group having 6 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination thereof Diamines are preferred, and diamines containing a group composed of an aromatic group having 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

上述芳香族基中，A是選自單鍵或可以由氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHCO-及它們的組合之基團為較佳，是選自單鍵、可以由氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO₂ -之基團為更佳，選自包括-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基團為進一步較佳。[Chemical formula 2]

In the above aromatic groups, A is selected from single bonds or aliphatic hydrocarbon groups with 1 to 10 carbons that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O ) ₂ -, -NHCO- and their combination groups are preferably selected from single bonds, alkylene groups with 1 to 3 carbons that can be substituted by fluorine atoms, -O-, -C (=O) -, -S-, -SO ₂ -are more preferably selected from groups including -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C( The divalent group in the group of _{CH 3} ) _{2-is further preferred.}

As the diamine, specifically 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-diaminocyclopentane Hexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis( Aminomethyl) cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone 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, double (3-amino-4-hydroxyphenyl) arsenic, bis(4-amino-3-hydroxyphenyl) arsenic, 4,4'-diamino-p-terphenyl, 4,4'-bis(4- Aminophenoxy) biphenyl, bis[4-(4-aminophenoxy)phenyl] chrysene, bis[4-(3-aminophenoxy) phenyl] chrysene, bis[4-( 2-aminophenoxy) phenyl] chrysene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1, 3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-di Amino diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl , 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'- Diaminobiphenyl, 9,9'-bis(4-amine Phenyl) pyrene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonium, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6 -Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine , 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene , Diaminobenzotrifluoride, diaminoanthraquinone, 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-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) )-3,5-Dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoro Propane, 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)diphenyl sulfide, 4 ,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoro (Methyl) biphenyl, at least one diamine among 2,2',5,5',6,6'-hexafluorotolidine and 4,4'''-diaminotetrabiphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[Chemical formula 3]

[Chemical formula 4]

In addition, as a preferred example, diamines having at least two alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine which combines either or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and it is more preferable that it does not contain an aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) Ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but It is not limited to these. The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[Chemical formula 5]

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

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ in the formula (2) is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L includes an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and A group of a combination of two or more of the above. Ar is preferably a phenylene group, L is an aliphatic hydrocarbon group with 1 or 2 carbons which may be substituted by a fluorine atom, and -O-, -CO-, -S- or -SO ₂ -is more preferred. Among them, the aliphatic hydrocarbon group is preferably an alkylene group.

式（51）中，R¹⁰ ～R¹⁷ 分別獨立地為氫原子、氟原子或1價有機基，R¹⁰ ～R¹⁷ 中的至少一個是氟原子、甲基或三氟甲基。 作為R¹⁰ ～R¹⁷ 的1價有機基，可列舉碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 式（61） [化學式7]

式（61）中，R¹⁸ 及R¹⁹ 分別獨立地為氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可列舉2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該些可以使用一種或組合使用兩種以上。From the viewpoint of i-ray transmittance, R ¹¹¹ in the formula (2) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 6]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, ^{and at least one of R 10} to R ¹⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). 6) The fluorinated alkyl group and so on. Formula (61) [Chemical Formula 7]

In the formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound imparting the structure of formula (51) or (61) include 2,2'-dimethylbenzidine and 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（5）中，R¹¹² 是選自單鍵或可以由氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -、-NHCO-以及包括它們的組合之基團為較佳，是選自單鍵、可以由氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之組中之2價基團為進一步較佳。 ^{R 115} in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. Formula (5) [Chemical Formula 8]

In formula (5), R ¹¹² is selected from a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O- _{, -CO-, -S-, -SO 2} -, -NHCO- And groups including combinations thereof are preferred, and are selected from single bonds, alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO _2- The group is more preferably selected from among -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- The divalent group in the group is further preferred.

Formula (6) [Chemical Formula 9]

式（O）中，R¹¹⁵ 表示4價有機基。R¹¹⁵ 的較佳範圍與式（2）中的R¹¹⁵ 的定義相同，較佳範圍亦相同。 ^{Regarding R 115} in the formula (2), specifically, the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride and the like can be cited. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical Formula 10]

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

As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetra Carboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'oxydiphthalic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3, 3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4, 9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene Tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2, At least one of 3,4-benzenetetracarboxylic dianhydride and their C1-C6 alkyl group and/or C1-C6 alkoxy derivative.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples. [Chemical formula 11]

It is also preferable that at least one ^{of R 111} and R ¹¹⁵ in the formula (2) has a hydroxyl group. More specifically, as R ¹¹¹ , a residue of a diaminophenol derivative can be mentioned.

^{R 113} and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. ^{At least one of R 113} and R ¹¹⁴ in the formula (2) preferably contains a polymerizable group, and both of them preferably contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, and the like. As the polymerizable group, a photoradical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, oxomethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, Block isocyanate group, methylol group, amine group. As a radical polymerizable group having a polyimide precursor, a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like.

[Chemical formula 12]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a polyoxyalkylene group having 4 to 30 carbon atoms. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are more good. Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

^{R 113} or R ¹¹⁴ in formula (2) may be a monovalent organic group other than a polymerizable group. From the viewpoint of solubility with respect to an organic solvent, R ¹¹³ or R ¹¹⁴ in the formula (2) is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group. As a monovalent organic group, an aromatic group having 1, 2, or 3 (preferably 1) acidic groups bonded to the carbon atoms constituting the aryl group, and 1, 2, or having carbon atoms constituting the aryl group Three (preferably one) aralkyl groups of acidic groups are particularly preferred. Specifically, a C6-C20 aromatic group which has an acidic group, and a C7-25 aralkyl group which has an acidic group are mentioned specifically,. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be cited. The acidic group is preferably a hydroxyl group. R ¹¹³ or R ¹¹⁴ is a hydrogen atom, and a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group are more particularly preferred.

The carbon number of the alkyl group represented ^{by R 113} or R ¹¹⁴ in formula (2) is preferably 1-30. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. , Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. ^{The cyclic alkyl group represented by R 113} or R ¹¹⁴ in formula (2) may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Aceto, dicyclohexyl and pinenyl (pinenyl). Among them, the cyclohexyl group is the most preferable from the viewpoint of achieving high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. ^{As the aromatic group represented by R 113} or R ¹¹⁴ in formula (2), specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentene ring, indene ring, azulene ring, heptene ring Ring, dicyclopentacene ring, perylene ring, fused pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, phenanthrene ring, terphenylene ring, pyrene ring, biphenyl ring, pyrrole Ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoleazine ring, indole ring, benzofuran ring, benzothiophene ring , Isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring , Phenanthroline ring, thianthracene ring, chromene ring, dibenzopyran ring, phenoxathi ring, phenothiazine ring or phenanthrazine ring. The benzene ring is the best.

^{When R 113} in formula (2) is a hydrogen atom, or when R ¹¹⁴ in formula (2) is a hydrogen atom, the polyimide precursor can form a co-polymer with a tertiary amine compound having ethylenically unsaturated bonds. Conjugate base. Examples of tertiary amine compounds having such ethylenically unsaturated bonds include N,N-dimethylamino propyl methacrylate.

In addition, in the polyimide precursor, it is also preferable to have a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure can be copolymerized with the polyimide precursor. Specifically, as the diamine component used to introduce the aliphatic group of the silicone structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethyl Base pentasiloxane and so on.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基，R¹¹³ 及R¹¹⁴ 中的至少一個是包含聚合性基之基團，是聚合性基為較佳。The repeating unit represented by the formula (2) is preferably the repeating unit represented by the following formula (2-A). That is, at least one of the polyimide precursors is preferably a precursor having a repeating unit represented by formula (2-A). With this structure, the width of exposure latitude can be further increased. Formula (2-A) [Chemical Formula 13]

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

Of formula (2-A) in ^{A 1, A 2, R 111} , R 113 and R ¹¹⁴ each independently have the formula ^{A 1, A 2, R 111} , the same as R ¹¹³ and R ¹¹⁴ defined in (2), more The optimal range is also the same. ¹¹² same as defined in formula R ¹¹² and R (5) in the formula (2-A), the preferred range is also the same.

In the polyimide precursor, the repeating unit represented by formula (2) may be one type or two or more types. In addition, the polyimide precursor may include structural isomers of the repeating unit represented by formula (2). Furthermore, in addition to the repeating unit represented by the above formula (2), the polyimide precursor may further include another repeating unit.

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total repeating unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, represented by formula (2) Polyimide precursor of repeating unit.

The polyimide precursor is preferably obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is more preferably obtained by halogenating the dicarboxylic acid or dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. The polyimide precursor can be obtained by the following methods, for example, a method of reacting a tetracarboxylic dianhydride with a diamine compound (partially replaced by a blocking agent as a monoamine) at a low temperature, and a tetracarboxylic acid at a low temperature. A method of reacting acid dianhydride (partially replaced by a blocking agent as an acid anhydride or monoacid chloride or monoactive ester compound) with a diamine compound, after the diester is obtained from tetracarboxylic dianhydride and alcohol, in the presence of a condensing agent Under the method of reacting with diamine (part of the capping agent as a monoamine), after obtaining the diester from tetracarboxylic dianhydride and alcohol, the remaining carboxylic acid is chlorinated to make it react with the diamine ( Substituting part of the capping agent as a monoamine) reaction method and other methods. In the production method of the polyimide precursor, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When producing the polyimide precursor, in order to further improve the storage stability, it is preferable to seal it with a blocking agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride, and a monoactive ester compound. Among these, it is more preferable to use monoamines. As preferred compounds of monoamines, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyl Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-amine Thiophenol and so on. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

When the polyimide precursor is manufactured, a process for precipitation of solids may be included. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation. Then, by drying the polyimide precursor, a powdery polyimine precursor can be obtained.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9200 to 11200. The dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is more preferred, 3.2 or less is more preferred, and 3.1 or less is more preferred. More preferably, 3.0 or less is even more preferable, and 2.95 or less is especially more preferable.

式（4）中，R¹³¹ 表示2價有機基，R¹³² 表示4價有機基。 當具有聚合性基時，R¹³¹ 及R¹³² 中的至少一方可以具有聚合性基，如下述式（4-1）或式（4-2）所示那樣可以於聚醯亞胺的末端具有聚合性基。(Polyimine) The polyimine is not particularly limited as long as it is a polymer compound having an imine ring. The polyimide is preferably a compound represented by the following formula (4), is a compound represented by the formula (4), and more preferably has a polymerizable group. Formula (4) [Chemical Formula 14]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When it has a polymerizable group, ^{at least one of R 131} and R ¹³² may have a polymerizable group. As shown in the following formula (4-1) or formula (4-2), it may have a polymerizable group at the end of the polyimide. Sex-based.

式（4-1）中，R¹³³ 是聚合性基，其他基團與式（4）的定義相同。Formula (4-1) [Chemical Formula 15]

In the formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same definitions as in the formula (4).

式（4-2）中，R¹³⁴ 及R¹³⁵ 中的至少一個是聚合性基，另一個是有機基，其他基團與式（4）的定義相同。Formula (4-2) [Chemical formula 16]

In the formula (4-2), ^{at least one of R 134} and R ¹³⁵ is a polymerizable group, the other is an organic group, and the other groups have the same definitions as in the formula (4).

The preferable polymerizable group possessed by polyimine is the same as the polymerizable group exemplified as the polymerizable group that ^{R 113} and R ^{114 in formula (2) in the polyimide precursor may contain.}

^{R 131} in formula (4) represents a divalent organic group. ^{As the divalent organic group, the same divalent organic group as R 111} in the formula (2) is exemplified, and the preferred range is also the same. Moreover, as R ¹³¹ , the diamine residue remaining after removing the amine group of the diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example ^{of R 111} in the formula (2) of the polyimide precursor can be cited.

From the viewpoint of more effectively suppressing warpage during firing, R ¹³¹ in formula (4) is preferably a diamine residue having at least two alkylene glycol units in the main chain. It is more preferable to combine any one or two of an ethylene glycol chain and a propylene glycol chain in one molecule to include two or more diamine residues, and still more preferably a diamine residue that does not include an aromatic ring.

As a diamine that combines any one or two of an ethylene glycol chain and a propylene glycol chain in one molecule to include two or more diamines, the same specific examples as the diamine ^{capable of derivatizing R 111 in formula (2) can be cited.} , But not limited to this.

^{R 132} in the formula (4) represents a tetravalent organic group. As the tetravalent organic group represented by R ^{132 , the same as R 115} in formula (2) is exemplified, and the preferred range is also the same. ^{For example, the four bonds of the tetravalent organic group of the following structure exemplified as R 115} in the formula (2) are bonded to a part of the four -C(=O)- in the above formula (4) to form Condensed ring. [Chemical formula 17]

^{Examples of R 132} in formula (4) include tetracarboxylic acid residues remaining after removing anhydride groups from tetracarboxylic dianhydride. As a specific example, an example ^{of R 115} in the formula (2) of the polyimide precursor can be cited. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one ^{of R 131} and R ¹³² in the formula (4) has a hydroxyl group. More specifically, as R ¹³¹ in formula (4), 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl) Base) hexafluoropropane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA -1) ~ (DA-18) are exemplified as preferred examples. ^{As R 132} in the formula (4), the above-mentioned (DAA-1) to (DAA-5) are exemplified as preferable examples.

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

In addition, for the purpose of improving adhesion to the substrate, an aliphatic group having a siloxane structure can be copolymerized with polyimide. Specifically, as the diamine component used to introduce an aliphatic group having a silicone structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl) Methyl pentasiloxane and so on.

Moreover, in order to improve the storage stability of the photosensitive resin composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride, and a monoactive ester compound. Among these, it is more preferable to use monoamine. Preferred examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 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 of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

The imidization rate of polyimide is preferably 85% or more, and more preferably 90% or more. The imidization rate is 85% or more, whereby the film shrinkage caused by the closed loop generated when the imidization is heated by heating is reduced, and the occurrence of substrate warping can be suppressed.

Polyimide includes not only a whole R or R ^{131 is} the repeating unit represented by the above formula (4) of ^132, may also comprise two or more different types of repeating units, or R ^{131 is} R ^132. Furthermore, in addition to the repeating unit represented by the above formula (4), the polybenzoxazole may also include other types of repeating units.

Regarding the polyimide, it can be produced by synthesizing the polyimine precursor and then heating and cyclizing it, or it can be synthesized directly. Polyimine can be synthesized by the following method, that is, the polyimine precursor is obtained, and the known method of the imine reaction method is used to complete the imidization method or the imidization reaction is stopped on the way, and A method of introducing a part of the imine structure, and then a method of pulverizing the completely imidized polymer and the polyimide precursor, thereby introducing a part of the imine structure.

As a commercially available product of polyimide, Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN) are exemplified.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. In addition, when two or more types of polyimines are contained, the weight average molecular weight of at least one type of polyimines is preferably within the above-mentioned range.

式（3）中，R¹²¹ 表示2價有機基，R¹²² 表示4價有機基，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基。(Polybenzoxazole Precursor) The polybenzoxazole precursor is not particularly limited in its kind, etc., but preferably contains a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 18]

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

R ¹²³ and R ¹²⁴ in formula (3) have the ^{same definitions as R 113} in formula (2), and their preferred ranges are also the same. That is, it is preferable that at least one ^{of R 123} and R ^{124 in the formula (3) is a polymerizable group.}

^{R 121} in the formula (3) represents a divalent organic group. As the divalent organic group represented by R ^121, it is preferable to include at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing straight-chain or branched (preferably straight-chain) aliphatic groups are preferred, including straight-chain or branched (preferably straight-chain) aliphatic groups and two A COOH dicarboxylic acid is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, particularly preferably 4-15, and 5-10 To be further preferred. The straight-chain aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid , Tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoro Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methyl Glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctane Diacid, azelaic acid, sebacic acid, hexadecanofluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, behenedioic acid, tricosanedioic acid , Tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triaconanedioic acid, three Undecanedioic acid, tridodecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

（式中，Z是碳數1～6的烴基，n是1～6的整數。）[Chemical formula 19]

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

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

上述芳香族基中，A表示選自包括-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基團。[Chemical formula 20]

In the above aromatic group, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -and -C(CH ₃ ) A divalent group in the group _{2 -.}

As specific examples of dicarboxylic acids containing aromatic groups, 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid are preferred.

^{R 122} in the formula (3) represents a tetravalent organic group. As the tetravalent organic group represented by R ^{122 , the same as R 115} in the above formula (2) is exemplified, and the preferred range is also the same. ^{R 122} in formula (3) is further preferably a group derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'- Dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfide, bis-( 3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl) ) Hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-( 4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxy Benzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-di Amino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

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

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

Formula (A-s)

In formula (As), R ₁ is selected from alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or the following formula (A -The organic group in the group of sc).

In the formula (As), R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. In the formula (As), R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示與由上述式（A-s）表示之二胺基苯酚衍生物的胺基苯酚的芳香環鍵結之情況。）Formula (A-sc) [Chemical formula 23]

(In the formula (A-sc), * represents the condition of bonding to the aromatic ring of the aminophenol of the diaminophenol derivative represented by the above formula (As).)

In the above formula (As), the ortho position of the phenolic hydroxyl group, that is, it is considered to _{have a substituent at R 3} , which can make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and further increase when hardened at low temperature. Considering the effect of high cyclization rate, it is particularly good.

In addition, in the above formula (As), when R ₂ is an alkyl group, and R ₃ is an alkyl group, it is preferable to maintain high transparency to i-rays and achieve a high cyclization rate when cured at low temperature. .

Furthermore, in the above formula (As), it _{is more preferable that R 1} is an alkylene group or a substituted alkylene group. Specific examples of the alkylene and substituted alkylene represented by R _{1 include -CH 2} -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -CH (CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-etc., where -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -It can also maintain high transparency to i-rays and the effect of high cyclization rate when cured at low temperature, while obtaining a polybenzoxazole precursor that has sufficient solubility with respect to solvents and an excellent balance, Therefore it is better.

As a method for producing the diaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 of JP 2013-256506 A and Example 1 (paragraphs 0189 to 0190), and the These contents are incorporated into this manual.

Specific examples of the structure of the diaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, and these contents are incorporated into this specification . Of course, it is not limited to these.

In addition to the repeating unit represented by the above formula (3), the polybenzoxazole precursor may also include another repeating unit. From the viewpoint of suppressing the warpage of the substrate accompanying the ring closure of the polybenzoxazole precursor, the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another repeating unit: Better.

式（SL）中，Z具有a結構和b結構，R^1s 是氫原子或碳數1～10的烴基，R^2s 是碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少一個是芳香族基，剩餘是氫原子或碳數1～30的有機基，該些可以分別相同或不同。a結構及b結構的聚合可以是嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構是5～95莫耳%，b結構是95～5莫耳%，a結構及b結構之和是100莫耳%。[Chemical formula 24]

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

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the structure b are phenyl groups. In addition, the molecular weight of the diamine residue represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. Setting the molecular weight of the diamine residue represented by the formula (SL) within the above range can more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and can also suppress the warpage of the substrate. The effect and the effect of improving the solubility of the solvent.

When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferable to include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in the formula (2) can be given.

In the weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when the composition described later is used, it is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9200 to 11200. The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited. For example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is more preferable, 2.3 or less is more preferable, and 2.2 or less is It is even better.

式（X）中，R¹³³ 表示2價有機基，R¹³⁴ 表示4價有機基。 當具有聚合性基時，R¹³³ 及R¹³⁴ 中的至少一個可以具有聚合性基，如由下述式（X-1）或式（X-2）表示那樣可以於聚苯并噁唑的末端具有聚合性基。(Polybenzoxazole) The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring. Polybenzoxazole is preferably a compound represented by the following formula (X), a compound represented by the following formula (X), and a compound having a polymerizable group is more preferred. [Chemical formula 25]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When it has a polymerizable group, ^{at least one of R 133} and R ¹³⁴ may have a polymerizable group, and it may be at the end of the polybenzoxazole as represented by the following formula (X-1) or formula (X-2) Has a polymerizable group.

式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一個是聚合性基，另一個是有機基，另一基團與式（X）的定義相同。Formula (X-1) [Chemical Formula 26]

In the formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polymerizable group, the other is an organic group, and the other group has the same definition as the formula (X).

式（X-2）中，R¹³⁷ 是聚合性基，其他為取代基，其他基團與式（X）的定義相同。Formula (X-2) [Chemical Formula 27]

In the formula (X-2), ^R137 is a polymerizable group, the others are substituents, and the other groups have the same definitions as in the formula (X).

The polymerizable group preferably possessed by polybenzoxazole has the same definition as the polymerizable group described by the polymerizable group possessed by the polyimide precursor described above.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group can be mentioned. As a specific example, an example ^{of R 121} in the formula (3) of the polybenzoxazole precursor can be cited. In addition, this preferred example has the same definition as ^{R 121.}

R ¹³⁴ represents a tetravalent organic group. ^{Examples of the tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. In addition, this preferred example has the same definition as ^{R 122.} For example, ^{the four bonds of the tetravalent organic group exemplified as R 122} are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 28]

The oxazolation rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. Since the oxazolidization rate is 85% or more, the film shrinkage caused by the closed loop generated during oxazolidization due to heating becomes smaller, and the occurrence of warpage can be effectively suppressed.

Polybenzoxazole not only includes all of the repeating units represented by the above formula (X) based on one kind of R ¹³³ or R ^{134 , but may also include two or more different kinds of R 133} or R ¹³⁴ groups which are derived from the above formula ( X) represents the repeating unit. Furthermore, in addition to the repeating unit represented by the above formula (X), the polybenzoxazole may contain another repeating unit.

Polybenzoxazole is obtained, for example, by reacting a diaminophenol derivative with a compound selected from ^{the dicarboxylic acid containing R 133} and the dicarboxylic acid dichloride and dicarboxylic acid derivative of the above-mentioned dicarboxylic acid, etc. The polybenzoxazole precursor is obtained by oxazolation using a known oxazolation reaction method. In addition, in the case of a dicarboxylic acid, in order to increase the reaction yield, etc., an active ester-type dicarboxylic acid derivative that has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole and the like can be used.

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

(Other photosensitive resin) Even if it is a photosensitive resin other than the above, this invention can be applied. As other photosensitive resins, epoxy resins, phenol resins, and benzocyclobutane-based resins can be used.

<<<Polymerizable compound>>> It is preferable that the resin has a polymerizable group, or the photosensitive resin composition contains a polymerizable compound. With this structure, a cured film with more excellent heat resistance can be formed. The polymerizable compound is a compound having a polymerizable group, and it is possible to use a known compound capable of crosslinking reaction by a radical, an acid, a basic group, or the like. As a polymerizable group, the polymerizable group etc. demonstrated using the said polyimide precursor are illustrated. The polymerizable compound may contain only one type or two or more types. Regarding the polymerizable compound, for example, it is any one of chemical forms such as monomers, prepolymers, oligomers, their mixtures, and their multimers.

In the present invention, the monomer-type polymerizable compound (hereinafter referred to as polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low-molecular compound, and a low-molecular compound with a molecular weight of 2000 or less is preferable, a low-molecular compound with a molecular weight of 1500 or less is more preferable, and a low-molecular compound with a molecular weight of 900 or less is more preferable. In addition, the molecular weight of the polymerizable monomer is usually 100 or more. In addition, the oligomer-type polymerizable compound is typically a polymer with a relatively low molecular weight, and preferably a polymer with 10 to 100 polymerizable monomers bonded thereto. The weight average molecular weight of the oligomer type polymerizable compound is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

The number of functional groups of a polymerizable compound refers to the number of polymerizable groups in one molecule. From the viewpoint of developability, the photosensitive resin composition preferably contains at least one bifunctional or more polymerizable compound including two or more polymerizable groups, and more preferably contains at least one trifunctional or more polymerizable compound. From the viewpoint of forming a three-dimensional crosslinked structure to improve heat resistance, the photosensitive resin composition preferably contains at least one trifunctional or higher polymerizable compound. In addition, it may be a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher polymerizable compound.

As a polymerizable compound, a compound containing a group having an ethylenically unsaturated bond; a compound having a methylol group, an alkoxymethyl group or an oxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine Compounds are preferred.

(Compounds containing groups having ethylenically unsaturated bonds) As the groups having ethylenically unsaturated bonds, styryl, vinyl, (meth)acrylic and (meth)allyl groups are preferred , (Meth)acrylic acid group is more preferable.

As a specific example of a compound containing a group having an ethylenically unsaturated bond, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or its The esters, amides, and their multimers are preferably esters of unsaturated carboxylic acids and polyhydric alcohols, and amides of unsaturated carboxylic acids and polyamine compounds, and their multimers. In addition, addition reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional isocyanates or epoxy groups with affinity substituents such as hydroxyl, amine, and mercapto groups can also be preferably used, and mono Dehydration condensation reaction product of functional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reactants of unsaturated carboxylic acid esters or amides having a detachable substituent such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used.

As specific examples of monomers of esters of polyhydric alcohols and unsaturated carboxylic acids, as acrylates, there are ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetraethylene glycol diacrylate. Methyl glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(acryloxypropyl) ether, trimethylol Ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, two Pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene oxyethyl) heterotrimerization Cyanate ester, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate oligomer, etc.

As methacrylates, there are tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double 〔 P(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p(methacryloxyethoxy)phenyl]dimethylmethane, etc.

As itaconates, there are ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, four Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, etc.

As the crotonate, there are ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetra-dicrotonate, and the like.

As isocrotonic acid esters, there are ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

As examples of other esters, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334, and Japanese Patent Application Publication No. 57-196231 can also be preferably used. , Or those having an aromatic skeleton described in Japanese Patent Application Publication No. 59-5240, Japanese Patent Application Publication No. 59-5241, Japanese Patent Application Publication No. 2-226149, Japanese Patent Application Publication No. 1-165613 Those that contain an amine group, etc. are described.

In addition, as specific examples of the monomer of the polyamine compound and the amide of the unsaturated carboxylic acid, there are methylene bis-acrylamide, methylene bis-methacrylamide, and 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

As an example of other preferable amide-based monomers, those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726 can be cited.

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

Furthermore, in the present invention, as the compound containing a group having an ethylenically unsaturated bond, the compound described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be preferably used.

Furthermore, as a compound containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. ; Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol four (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ) Ether, tris (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, etc. are added to polyfunctional alcohols with ethylene oxide or propylene oxide for (meth)acrylic acid Esterification, such as (meth)acrylate urethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Publication No. 51-37193, Japan The polyester acrylates described in Japanese Patent Application Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Application Publication No. 52-30490 are used as reaction products of epoxy resin and (meth)acrylic acid. Polyfunctional acrylates or methacrylates, such as epoxy acrylates, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group, such as a polyfunctional carboxylic acid and glycidyl (meth)acrylate react, are mentioned. In addition, as other preferred polymerizable compounds containing a group having an ethylenically unsaturated bond, Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used. The compound or cardo resin described has a sulphur ring and two or more ethylenically unsaturated bond-containing groups. 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, or Japanese Patent Application Publication No. 2 Vinylphosphonic acid-based compounds described in -25493 Gazette, etc. In addition, in certain cases, the perfluoroalkyl group-containing structure described in JP 61-22048 A can be suitably used. Furthermore, it is also possible to use those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

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

[Chemical formula 29]

[Chemical formula 30]

In each of the above formulas, n is an integer of 0-14, and m is an integer of 1-8. A plurality of R and T in the molecule may be the same or different. In each of the polymerizable compounds represented by the above-mentioned formulas (MO-1)～(MO-5), at least one of the plural Rs is represented by -OC (=O) CH=CH ₂ or, -OC (=O ) C(CH ₃ )=CH ₂ represents a group. In the present invention, as a specific example of the compound containing a group having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5), Japanese Patent Application Publication No. 2007-269779 can be preferably used The compound described in paragraphs 0248 to 0251 of the publication.

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

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used, and these contents can be incorporated in this specification. In particular, as a preferable aspect, the compounds described in paragraphs 0128 to 0130 of the above publication are exemplified.

As a compound containing a group having an ethylenically unsaturated bond, dipentaerythritol triacrylate (as a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa( Meth) acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) and these (meth)acrylic acid groups are bonded via ethylene glycol residues and propylene glycol residues. good. It is also possible to use their oligomer types. Moreover, as a preferable example, the pentaerythritol derivatives and/or dipentaerythritol derivatives of the above-mentioned formula (MO-1) and (MO-2) can also be cited.

Commercial products of polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as a bifunctional acrylic having 4 ethoxy chains. SR-209 manufactured by Sartomer Company, Inc. of methyl ester, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxy chains, as DPCA-60 with 3 isobutylene groups Trifunctional acrylate TPA-330, 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.

As a compound containing a group having an ethylenically unsaturated bond, such as Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765 Urethane acrylates as described in the gazette, Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 The urethane compounds having an ethylene oxide-based skeleton described in the gazette are also preferable. Furthermore, as the polymerizable compound, those having an amino group structure in the molecule or those described in JP-A 63-277653, JP-A 63-260909, and JP-A 1-105238 can also be used. Sulfide structure of addition polymerizable monomers.

The compound containing a group having an ethylenically unsaturated bond may be a multifunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among the polyfunctional monomers having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds react with non-aromatic carboxylic anhydrides to have many acid groups Functional monomers are more preferable. Particularly preferably, among the polyfunctional monomers having an acid group by reacting unreacted hydroxyl groups of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercially available product, for example, as a polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., M-510, M-520, and the like can be cited. The polyfunctional monomer having an acid group may be used singly or in combination of two or more. Furthermore, if necessary, a multifunctional monomer having no acid group and a multifunctional monomer having an acid group can be used in combination. The preferable acid value as a polyfunctional monomer having an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the polyfunctional monomer is within the above-mentioned range, the production and handling properties are excellent, and furthermore, the developability is excellent. In addition, the polymerizability is also good.

From the viewpoint of good polymerizability and heat resistance, the content of the compound containing a group having an ethylenically unsaturated bond is preferably 1 to 50% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The compound containing a group having an ethylenically unsaturated bond may be used singly or in combination of two or more. In addition, the mass ratio of the resin to the compound containing the ethylenically unsaturated bond (resin/polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90 /10～50/50 is the best. As long as the mass ratio of the resin and the compound containing a group having an ethylenically unsaturated bond is within the above range, a cured film with more excellent polymerizability and heat resistance can be formed.

(The compound having a hydroxymethyl group, an alkoxymethyl group, or an oxymethyl group) As a compound having a hydroxymethyl group, an alkoxymethyl group or an oxymethyl group, a compound represented by the following formula (AM1) is preferred.

（式中，t表示1～20的整數，R⁴ 表示碳數1～200的t價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM1) [Chemical Formula 31]

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

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

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

It is preferable that the compound represented by formula (AM1) is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin. More preferably, it is 10 parts by mass or more and 35 parts by mass or less. In addition, all polymerizable compounds contain 10% by mass or more and 90% by mass or less of the compound represented by the following formula (AM4), and all thermal crosslinking agents contain 10% by mass or more and 90% by mass or less by the following formula The compound represented by (AM5) is also preferred.

（式中，R⁴ 表示碳數1～200的2價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM4) [Chemical Formula 33]

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

（式中，u表示3～8的整數，R⁴ 表示碳數1～200的u價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM5) [Chemical Formula 34]

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

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

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

By setting it as this range, when the photosensitive resin composition layer is formed on the uneven|corrugated board|substrate, the occurrence of cracks is further reduced. In addition, it can have excellent pattern processability, and the 5% mass reduction temperature is 350°C or higher, more preferably 380°C or higher, and has high heat resistance. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (The above is the product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol, 2,6-Dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-acetoxymethyl-p-cresol (2,6-diacethoxymethyl-p-cresol) Wait.

Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are product names, manufactured by Sanwa Chemical Co., Ltd.).

<<<Photopolymerization initiator>>> The photosensitive resin composition may contain a photopolymerization initiator. In particular, since the photosensitive resin composition contains a photoradical polymerization initiator, the photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then light is irradiated to generate free radicals. It causes hardening and can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that by exposing the photosensitive resin composition layer through a light mask having a pattern for shielding only the electrode portion, it is possible to easily create regions with different solubility in accordance with the electrode pattern.

The photopolymerization initiator is not particularly limited as long as it has the ability to start the polymerization reaction (crosslinking reaction) of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable that the light from the ultraviolet region has sensitivity to the visible region. In addition, it can be an active agent that interacts with a light-excited sensitizer and generates active free radicals. It is preferable that the photopolymerization initiator contains at least one compound having at least about 50 molar absorption coefficient in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, it is preferable to measure with an ultraviolet-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, known compounds can be used without limitation, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), acyl groups Phosphine compounds such as phosphine oxide, oxime compounds such as hexaarylbiimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxybenzene Ethyl ketones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc.

Examples of halogenated hydrocarbon compounds having a triazine skeleton include compounds described in Wakabayashi et al., "Bull. Chem. Soc. Japan", 42, 2924 (1969), British Patent No. 1388492 The compound described in the specification, the compound described in Japanese Unexamined Patent Publication No. 53-133428, the compound described in the specification of German Patent No. 3337024, FC Schaefer et al. "Journal of Organic Chemistry (J. Org) Chem.)", 29, 1527 (1964), the compound described in JP-A 62-58241, the compound described in JP 5-281728, JP-H The compound described in 5-34920 gazette, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

As the compound described in the specification of U.S. Patent No. 4212976, for example, a compound having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-Trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -Tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl- 1,3,4-oxadiazole etc.) etc.

In addition, examples of photopolymerization initiators other than the above include the compounds described in paragraph 0086 of Japanese Patent Application Publication No. 2015-087611, Japanese Patent Application Publication No. 53-133428, Japanese Patent Application Publication No. 57-1819, and Japan. The compounds described in Japanese Patent Publication No. 57-6096 and US Patent No. 3615455 are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content is incorporated in this specification. KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used among commercially available products.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (product names: all manufactured by BASF Corporation), which are commercially available products, can be used. As the aminoacetophenone-based initiator, it is also possible to use the compound described in JP 2009-191179 A whose maximum absorption wavelength matches the wavelength of 365 nm or 405 nm. Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation), which are commercially available products, can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like are exemplified.

As the photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among the oxime ester-based compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a thermal base generator, so it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842, the compounds described in JP 2000-80068, and the compounds described in JP 2006-342166 can be used. . As preferred oxime compounds, for example, the following compounds, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propane Acetyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2 -Benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropan-1-one, etc. [Chemical formula 36]

As the oxime compound, various documents of JCS Perkin II (1979) pp.1653-1660, JCS Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232 can be cited The compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797, JP 2006-342166, International Publication WO2015 /036910 Bulletin, the compound described in each bulletin. Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMERN-1919 (made by ADEKA CORPORATION, Japanese Patent Publication No. 2012-14052 The photopolymerization initiator described in the gazette 2). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA Corporation) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used.

關於最佳之肟化合物，可列舉日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物、日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。In addition, it is possible to use the compound described in Japanese Patent Publication No. 2009-519904 with an oxime linked to the N position of the carbazole ring, and the compound described in U.S. Patent No. 7626957 in which a heterosubstituent is introduced at the benzophenone site. The compound, the compound described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039, the ketoxime compound described in International Publication WO2009-131189, in which the nitro group is introduced into the pigment site, in the molecule The compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton, the compound described in Japanese Patent Application Laid-Open No. 2009-221114, etc. having a maximum absorption at 405 nm and having good sensitivity to a g-ray light source. In addition, it is also possible to preferably use the cyclic oxime compounds described in JP 2007-231000 A and JP 2007-322744 A. From the viewpoint of high light absorption and high sensitivity, among the cyclic oxime compounds, in particular, the condensed carbazole dyes described in JP 2010-32985 A and 2010-185072 The cyclic oxime compound is also preferred. In addition, the compound described in JP 2009-242469 A, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be preferably used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) and the like described in paragraph 0101 of the 2013-164471 Bulletin. As specific examples, the following compounds can be cited. [Chemical formula 37]

As for the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and oxime compounds having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited. Wait.

式（I）中，R⁵⁰ 是碳數1～20的烷基；因1個以上的氧原子而中斷之碳數2～20的烷基；碳數1～12的烷氧基；苯基；由碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數1～12的烯基、因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R⁵¹ 是由式（II）表示之基團，或者是與R⁵⁰ 相同的基團，R⁵² ～R⁵⁴ 各自獨立地是碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式39]

式中，R⁵⁵ ～R⁵⁷ 與上述式（I）的R⁵² ～R⁵⁴ 相同。From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and phosphine compounds. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferred photopolymerization initiators are selected from the group consisting of trihalomethyl triazine compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, acetophenone compounds, particularly preferably selected from trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds At least one compound in the group is more preferred, a metallocene compound or an oxime compound is more preferred, and an oxime compound is even more particularly preferred. In addition, the photopolymerization initiator can also use N,N'-tetraalkyl groups such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler’s ketone). -4,4'-Diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones condensed with aromatic rings, benzoin such as alkyl ethers of benzoin Benzoin compounds such as ether compounds, benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used. [Chemical formula 38]

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

In the formula, R ⁵⁵ to R ⁵⁷ are the same as ^{R 52} to R ^{54 in the} above formula (I).

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

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

<<<Migration inhibitor>>> It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring). Ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring, etc.). Thiourea and mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazino derivative compounds. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion scavenger that traps anions such as halogen ions can also be used.

As other migration inhibitors, the antiseptic agents described in paragraph 0094 of JP 2013-15701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. The compound described in paragraph 0052 of -59656, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, etc.

Specific examples of migration inhibitors include 1H-1,2,3-triazole, 1H-1,2,4-triazole, and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the photosensitive resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass is more preferable. There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, it is preferable that the total of them is in the above-mentioned range.

<<<Polymerization inhibitor>>> The photosensitive resin composition used in the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6 -Tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-phenylenediphenylamine, 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-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above-mentioned range.

<<<Thermal base generator>>> The photosensitive resin composition used in the present invention may contain a thermal base generator. The type of the thermal base generator is not particularly limited, and it is preferable to include a thermal base generator. The thermal base generator includes an acidic compound selected from the group that generates a base heated to 40°C or higher and those having a pKa1 of 0-4 At least one of the ammonium salt of an anion and an ammonium cation. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later. By blending this compound, the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor can be carried out at a low temperature, and a composition with more excellent stability can be obtained. In addition, the thermal alkali generator does not generate alkali as long as it is not heated. Therefore, even if it coexists with the polyimide precursor and the polybenzoxazole precursor, it can suppress the polyimide precursor and the polyimide precursor during storage. The cyclization of polybenzoxazole precursors, etc., makes it more excellent in storage stability.

The thermal base generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40°C or higher, an anion having a pKa1 of 0 to 4, and an ammonium salt (A2) of an ammonium cation (A2). Regarding the acidic compound (A1) and the ammonium salt (A2), when heated, an alkali is generated. Therefore, the alkali generated by these compounds can promote the improvement of polyimide precursors and polybenzoxazole precursors, etc. Cyclization reaction, and can carry out the cyclization of polyimide precursors and polybenzoxazole precursors at low temperature. In addition, regarding these compounds, even if they coexist with polyimide precursors and polybenzoxazole precursors that are cyclized and hardened by an alkali, the polyimide precursors and polybenzoxazole precursors are hardly carried out as long as they are not heated. Cyclization of polybenzoxazole precursors, etc., makes it possible to prepare photosensitive resin compositions containing polyimide precursors and polybenzoxazole precursors with excellent stability. In addition, in this specification, an acidic compound refers to a compound whose value is less than 7 by measuring the following solution at 20°C with a pH (power of hydrogen) meter. The solution is to extract 1g of the compound into a container and add 50ml of ions. The mixed solution of exchange water and tetrahydrofuran (mass ratio of water/tetrahydrofuran=1/4) is obtained by stirring at room temperature for 1 hour.

In the present invention, the base 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 preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 165°C or lower. The lower limit of the alkali generation temperature is preferably 130°C or higher, and more preferably 135°C or higher. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120°C or higher, the alkali is unlikely to be generated during storage. Therefore, it is possible to prepare polyimide precursors and polybenzoxazole precursors with excellent stability Photosensitive resin composition such as objects. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor, the polybenzoxazole precursor, and the like can be lowered. Regarding the alkali generation temperature, for example, differential scanning calorimetry can be used to heat the compound in a pressure-resistant capsule at 5°C/min to 250°C, read the peak temperature of the heating peak with the lowest temperature, and use the peak temperature as the alkali Generate temperature for measurement.

In the present invention, the base produced 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 basicity, so it can further reduce the cyclization temperature of polyimine precursors and polybenzoxazole precursors. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher. In addition, the molecular weight of the base produced is preferably 80 to 2,000. It is more preferable that the lower limit is 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, it is preferable that the acidic compound (A1) contains one or more selected from the group consisting of ammonium salts and compounds represented by formula (101) or (102) described later.

In the present invention, 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 other than heating to 40°C or higher (preferably 120 to 200°C). ℃) when it produces compounds other than the acidic compounds of the base.

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁷ 表示烴基。式（101）及式（102）中的R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In the present invention, the ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or it may be present outside the molecule of the ammonium cation, but it is preferred to have it outside the molecule of the ammonium cation. In addition, the presence of the anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as an anion. Formula (101) Formula (102) [Chemical formula 40]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. ^{R 1} and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ^{7 in} formula (101) and formula (102) may be respectively bonded to form a ring.

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

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ^{7 have the} same definitions as in formula (101) or formula (102). In formulas (Y1-1) to (Y1-5), 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 0-5.

In the present invention, it is preferable that the ammonium salt has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. As long as the pKa1 of the anion is in the above range, polyimide precursors and polybenzoxazole precursors can be cyclized at low temperatures, and furthermore, the inclusion of polyimide precursors and polybenzoxazole precursors can be improved. Stability of photosensitive resin compositions such as materials. As long as pKa1 is 4 or less, the stability of the thermal alkali generator is good, and the generation of alkali is suppressed without heating, and the photosensitive resin composition containing polyimide precursors and polybenzoxazole precursors, etc. The stability of the material is good. As long as pKa1 is 0 or more, the generated alkali is not easily neutralized, and the cyclization efficiency of the polyimide precursor and the polybenzoxazole precursor is good. The type of anion is preferably one selected from the group consisting of carboxylic acid anion, phenol anion, phosphoric acid anion, and sulfuric acid anion, and carboxylic acid anion is more preferable from the viewpoint of compatibility of salt stability and thermal decomposition. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic anion. The carboxylic acid anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator that can further improve the stability, curability, and developability of a photosensitive resin composition including a polyimide precursor, a polybenzoxazole precursor, and the like. In particular, by using an anion of a divalent carboxylic acid, it is possible to further improve the stability, curability, and developability of a photosensitive resin composition including a polyimide precursor, a polybenzoxazole precursor, and the like. In the present invention, the carboxylic acid 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 still more preferable that it is 3.2 or less. According to this aspect, the stability of the photosensitive resin composition including the polyimide precursor, the polybenzoxazole precursor, and the like can be further improved. Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and can be found in Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) was used.

式（X1）中，EWG表示吸電子基。The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical formula 42]

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

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

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

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

式（XA）中，L¹⁰ 表示選自單鍵或伸烷基、伸烯基、芳香族基團、-NR^X -及它們的組合中之2價連接基，R^X 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical formula 44]

In the formula (XA), L ¹⁰ represents a divalent linking group selected from a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group , Alkenyl or aryl.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion. These can be used preferably.

[化學式46]

As specific examples of the thermal base generator, the following compounds can be cited. [Chemical formula 45]

[Chemical formula 46]

[Chemical formula 47]

When a thermal base generator is used, the content of the thermal base generator in the photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above-mentioned range.

金屬黏附性改良劑相對於樹脂100質量份較佳為0.1～30質量份，更佳為0.5～15質量份的範圍。藉由設為0.1質量份以上，硬化製程後的硬化膜與金屬層的黏附性變良好，藉由設為30質量份以下，硬化製程後的硬化膜的耐熱性、機械特性變良好。 金屬黏附性改良劑可以僅為一種，亦可以可兩種以上。當使用兩種以上時，其合計為上述範圍為較佳。<<<Metal adhesion improver>>> The photosensitive resin composition used in the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used in electrodes, wiring, and the like. Examples of the metal adhesion improver include the sulfides described in paragraphs 0046 to 0049 of JP 2014-186186 and paragraphs 0032 to 0043 of JP 2013-072935. As the metal adhesion improver, the following compounds (N-[3-(triethoxysilyl)propyl]maleic acid monoamide etc.) are also exemplified. [Chemical formula 48]

The metal adhesion modifier is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. By setting it as 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it as 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing process become better. There may be only one type of metal adhesion modifier, or two or more types. When two or more are used, it is preferable that the sum total is the above-mentioned range.

<<<Solvent>>> When the photosensitive resin composition used in the present invention is formed into a layer by coating, it is preferable to blend a solvent. Regarding the solvent, as long as the photosensitive resin composition can be formed into a layered form, known ones can be used without limitation. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfites. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl Butyl acid, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: alkoxy methyl acetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, methoxybutyl, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-Alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g., 3-methoxy propionate methyl, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: 2-alkoxypropionate Methyl ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, 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, pyruvate Ethyl ester, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl siloxol acetate, ethyl siloxol 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 acetic acid Ester, propylene glycol monopropyl ether acetate, etc. As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably mentioned. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned. As the sulfenites, dimethyl sulfenite can preferably be cited.

Regarding the solvent, from the viewpoint of improvement of the coating surface shape, etc., a form in which two or more types are mixed is also preferable. Among them, it is selected from the group consisting of 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cyrus acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol ethyl A mixed solution composed of two or more of acid esters, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone at the same time.

When the photosensitive resin composition has a solvent, regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition is preferably 5 to 80% by mass, 5 to 70% by mass is more preferable, and 10 to 60% by mass is particularly preferable. The content of the solvent can be adjusted by the coating method according to the desired thickness. For example, as long as the coating method is a spin coating method or a slit coating method, the content of the solvent having the solid content concentration in the above-mentioned range is preferable. As long as it is a spraying method, it is preferable to set it as 0.1 mass%-50 mass %, and it is preferable to set it as 1.0 mass%-25 mass %. By adjusting the content of the solvent according to the coating method, a photosensitive resin composition layer of a desired thickness can be uniformly formed. The solvent may be only one type or two or more types. When there are two or more solvents, it is preferable that the total amount is the above-mentioned range. Also, from the viewpoint of film strength, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide It is preferably less than 5% by mass relative to the total mass of the photosensitive resin composition, more preferably less than 1% by mass, particularly preferably less than 0.5% by mass, and more preferably less than 0.1% by mass.

＜＜＜Other additives＞＞＞ The photosensitive resin composition used in the present invention can add various additives, such as photobase generators and thermal polymerization initiators, as needed within the range that does not impair the effects of the present invention. , Thermal acid generators, silane coupling agents, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors Wait for cooperation. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator) The photosensitive resin composition used in the present invention may contain a photobase generator. Photobase generators are those that generate alkalis by exposure, and do not show activity under normal temperature and pressure conditions. However, as long as they are irradiated and heated by electromagnetic waves as an external stimulus, there is nothing special as long as they generate alkalis (alkaline substances). limited. The alkali generated by exposure functions as a catalyst when the polyimide precursor and the benzoxazole precursor are hardened by heating, and therefore can be preferably used in the negative type.

The content of the photobase generator is not particularly limited as long as a desired pattern can be formed, and it can be set to a normal content. The photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass relative to 100 parts by mass of the resin, more preferably in the range of 0.05 parts by mass to 25 parts by mass, and more preferably in the range of 0.1 parts by mass to 20 parts by mass Within the range of is further preferred. There may be only one type of photobase generator, or two or more types. When there are two or more photobase generators, the total range is preferably the above range.

In the present invention, those known as photobase generators can be used. For example, such as M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kadooka Masahiro, 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). Structures such as ammonium salts, such as those where the amidino moiety is latentized by the formation of carboxylic acids and salts, ionic compounds, urethane derivatives, and oxime esters in which alkali components are neutralized by the formation of salts Nonionic compounds such as urethane bonds or oxime bonds, such as compounds, acyl compounds, etc., in which the alkali component is latentized. The photobase generators that can be used in the present invention are not particularly limited, and known ones can be used. For example, carbamate derivatives, amide derivatives, imine derivatives, α-cobalt complexes, and imidazole derivatives can be used. Compounds, cinnamic acid amide derivatives, oxime derivatives, etc. Examples of photobase generators include photobase generators having a cinnamic acid amide structure as disclosed in Japanese Patent Application Publication No. 2009-80452 and International Publication No. WO2009/123122, such as those disclosed in Japanese Patent Application Publication No. 2006-189591 A photobase generator having a urethane structure as disclosed in Japanese Patent Application Publication No. 2008-247747 and Japanese Patent Application Publication No. 2008-247747 has an oxime as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581 Although the photobase generator of a structure, a carbamate structure, etc., it is not limited to this, A well-known photobase generator other than this can also be used. In addition, examples of photobase generators include compounds described in paragraphs 0185 to 0188, paragraphs 0199 to 0200, and paragraph 0202 of JP 2012-93746, and 0022 to paragraphs 0202 of JP 2013-194205. The compound described in paragraph 0069, the compound described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compound described in paragraph 0052 of International Publication WO2010/064631.

(Thermal polymerization initiator) The photosensitive resin composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be carried out during the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor. In addition, when the polyimide precursor and the polybenzoxazole precursor contain ethylenically unsaturated bonds, the cyclization and polyimide of the polyimide precursor and the polybenzoxazole precursor can be performed simultaneously The polymerization reaction of the precursor and the polybenzoxazole precursor can achieve a higher degree of heat resistance. Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A.

When the photosensitive resin composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator relative to the total solid content of the photosensitive resin composition is preferably 0.1-50% by mass, 0.1-30% by mass % Is more preferable, and 0.1-20% by mass is particularly preferable. 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, a cured film with more excellent heat resistance can be easily formed. The thermal radical polymerization initiator may be only one type or two or more types. When there are two or more thermal radical polymerization initiators, it is preferable that the total range thereof is the above-mentioned range.

(Thermal acid generator) The photosensitive resin composition used in the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating, promotes the cyclization of the polyimide precursor and the polybenzoxazole precursor, and improves the mechanical properties of the cured film. Furthermore, the thermal acid generator has the function of promoting crosslinking of at least one compound selected from the group consisting of a compound having a methylol group, an alkoxymethyl group or an oxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound The effect of the reaction.

As an example of a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.

In addition, as the thermal acid generator, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor, and more preferably 0.1 parts by mass or more. Since the content is 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of the cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is particularly preferable. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above-mentioned range.

(Silane Coupling Agent) The photosensitive resin composition used in the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate. Examples of silane coupling agents include the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and JP 2014 -191252, the compound described in paragraphs 0060 to 0061, the compound described in JP 2014-41264, paragraphs 0045 to 0052, and the compound described in international publication WO2014/097594, paragraph 0055. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. The silane coupling agent is preferably in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the resin, and more preferably in the range of 1 to 10 parts by mass. If it is 0.1 parts by mass or more, more sufficient adhesion to the substrate can be imparted, and if it is 20 parts by mass or less, problems such as increase in viscosity during storage at room temperature can be further suppressed. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above-mentioned range.

(Sensitizing Dye) The photosensitive resin composition used in the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the amine generator, thermal radical polymerization initiator, and photopolymerization initiator cause chemical changes to decompose, and generate radicals, acids, or bases.

As an example of a preferable sensitizing dye, those belonging to the following compound classes and having an absorption wavelength in the region of 300 nm to 450 nm can be cited. For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, terylene, 9.10-dialkoxyanthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rose red B , Rose Bengal), thioxanthones (for example, 2,4-diethylthioxanthone), cyanines (for example, thiocarbocyanine, oxacarbocyanine), merocyanines (Such as merocyanine, carbocyanine), thiazides (such as thiazol, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acriflavin), anthraquinone (Such as anthraquinone), squaraine ylide (such as squaraine ylide), coumarin (such as 7-diethylamino-4-methylcoumarin), styrene Base benzenes, stilbene benzenes, carbazoles, etc.

When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the photosensitive resin composition is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, and 0.5-10 The mass% is more preferable. The sensitizing dye may be used singly, or two or more may be used.

(Chain transfer agent) The photosensitive resin composition used in the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, free radicals can be generated by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole Class etc.).

When the photosensitive resin composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01-20 parts by mass, more preferably 1-10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition Parts by mass, particularly preferably 1 to 5 parts by mass. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, it is preferable that the total range thereof is the above-mentioned range.

(Surfactant) From the viewpoint of improving coatability, various surfactants can be added to the photosensitive resin composition used in the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used.

When the photosensitive resin composition has a surfactant, the content of the surfactant relative to the total solid content of the photosensitive resin composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, it is preferable that the total range thereof is the above-mentioned range.

(Higher fatty acid derivatives) In order to prevent polymerization inhibition due to oxygen, the photosensitive resin composition used in the present invention may be added with higher fatty acid derivatives such as behenic acid or behenic acid amide after coating Partially exists on the surface of the composition during the drying process. When the photosensitive resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative relative to the total solid content of the photosensitive resin composition is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

<<<Characteristics of the photosensitive resin composition>>> Next, the characteristics of the photosensitive resin composition used in the present invention will be described. The photosensitive resin composition used in the present invention is preferably exposed to light to construct a cross-linked structure to reduce the solubility to an organic solvent. By having a crosslinked structure, when the photosensitive resin composition layer is laminated, the adhesion between the layers can be improved. In addition, the solubility of the photosensitive resin composition layer in the organic solvent is reduced by exposure, which is advantageous when a deeper groove or a deeper hole is provided when the number of layers is increased. From the viewpoint of coating surface properties, the moisture content of the photosensitive resin composition used in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass.

From the viewpoint of insulation, the photosensitive resin composition used in the present invention preferably has a metal content of less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably in the above-mentioned range. In addition, as a method of reducing the metal impurities accidentally included in the photosensitive resin composition, it can be cited as the raw material constituting the photosensitive resin composition, selecting a raw material with a low metal content, and filtering the raw material constituting the photosensitive resin composition. Filtration, lining the device with polytetrafluoroethylene, and distilling under the condition of suppressing pollution as much as possible.

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

<<Drying process>> In the manufacturing method of the laminate of the present invention, a process of drying the solvent after forming the photosensitive resin composition may be included. The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure Process> The manufacturing method of the laminate of the present invention includes an exposure process for exposing the photosensitive resin composition layer. The conditions of exposure are not particularly limited, but it is better to change the solubility of the developer with respect to the exposed portion of the photosensitive resin composition, and it is more preferable to be able to harden the exposed portion of the photosensitive resin composition. For example, with respect to the photosensitive resin composition layer, the exposure ^{is preferably 100 to 10,000 mJ/cm 2} in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190 to 1000 nm, and 240 to 550 nm is preferable.

Exposure can be performed by pattern exposure, or exposure can be performed by uniformly irradiating the entire surface.

<Development process> The manufacturing method of the laminate of the present invention includes a development process of developing the exposed photosensitive resin composition layer. The development process is preferably a negative development process. By performing a negative-tone development process, the unexposed part (non-exposed part) is removed. The development method is not particularly limited, and it is preferable that a desired pattern can be formed. For example, a development method such as stirring, spraying, dipping, and ultrasonic wave can be used. In the present invention, it is better to also perform a development process when the exposure is performed by uniform irradiation on the entire surface. The development is preferably performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed. Development based on organic solvents is preferred. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: alkoxy acetic acid Methyl methoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g., 3-methoxy propionate Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (examples ：Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate)), 2-alkoxy-2-methylpropionate And ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers , For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like. As the sulfenites, dimethyl sulfenite can preferably be cited. Among them, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 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 more preferred. The development time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and it can usually be performed at 20 to 40°C. After the treatment with the developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinse time is preferably 5 seconds to 1 minute.

<Curing process> The manufacturing method of the laminated body of this invention includes the curing process of hardening the photosensitive resin composition layer after a development process. Preferably, the curing process includes a temperature-rising process of raising the temperature of the photosensitive resin composition layer and a cooling process of cooling the photosensitive resin composition layer after the temperature-raising process.

Regarding the hardening process (especially the heating process and the holding process), from the viewpoint of preventing the decomposition of the resin, it is better to perform it in a low oxygen concentration environment by flowing inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 volume ppm or less, and preferably 20 volume ppm or less.

<<Temperature increase process>> The temperature increase process is a process of raising the temperature of the photosensitive resin composition layer to a temperature higher than the glass transition temperature. In the heating process, it is preferable to subject the resin (preferably a polyimide precursor and a polybenzoxazole precursor) contained in the photosensitive resin composition layer to a cyclization reaction. For example, in polyimide or polybenzoxazole, when heated together with a crosslinking agent, a three-dimensional network structure can be formed. In addition, curing of unreacted radical polymerizable compounds can also be performed. The final temperature of the heating process is preferably the imidization temperature of the resin contained in the photosensitive resin composition layer. The final temperature of the heating process is preferably the highest heating temperature. As the maximum heating temperature, 100 to 500°C is preferred, 150 to 450°C is more preferred, and 160 to 350°C is even more preferred. From the viewpoint of stress relaxation, in the method of manufacturing a laminate of the present invention, it is particularly preferable that the final temperature of the heating process is 250° C. or lower.

Regarding the temperature increase, it is preferable to proceed from a temperature of 20 to 150°C to the maximum heating temperature at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 11°C/min, and still more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated. The temperature at the start of heating is preferably 20 to 150°C, more preferably 20 to 130°C, and even more preferably 25 to 120°C. The temperature at the beginning of heating refers to the heating temperature at the beginning of the heating process up to the maximum heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature after drying is used, for example, the temperature is gradually increased from the boiling point of the solvent contained in the photosensitive resin composition-(30 to 200)°C For better.

Heating can be carried out in stages. As an example, the following pre-treatment process can be carried out, that is, the temperature is raised at 3°C/min until 25°C to 180°C, placed at 180°C for 60 minutes, and the temperature is raised at 2°C/min until 180°C to 200°C. Place it at ℃ for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and most preferably 120-185°C. In the pre-treatment process, it is also preferable to perform treatment while irradiating UV as described in US Patent No. 9159547. Through this pretreatment process, the characteristics of the cured film can be improved. The pretreatment process is preferably carried out in a relatively short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pre-treatment process can be a two-stage or more step, for example, the pre-treatment process 1 is performed in the range of 100-150°C, and then the pre-treatment process 2 is performed in the range of 150-200°C.

The heating process is preferably 20 to 200 minutes, more preferably 20 to 100 minutes, and particularly preferably 20 to 60 minutes.

<<Holding process>> In the method of manufacturing a laminate of the present invention, after the temperature rising process, before the cooling process, it is preferable to include a holding process of maintaining a holding temperature equal to the final temperature of the temperature rising process. After reaching the final temperature of the heating process, it is better to perform heating for 30 to 360 minutes at a holding temperature equal to the final temperature of the heating process, more preferably to perform heating for 30 to 300 minutes, and heating for 30 to 240 minutes It is particularly preferred, and heating for 60 to 240 minutes is further particularly preferred. The time required in the holding process is called holding time. The holding temperature in the holding process is preferably 150-450°C, and more preferably 160-350°C. From the viewpoint of stress relaxation, in the method of manufacturing the laminate of the present invention, it is particularly preferable that the holding temperature in the holding process is 250° C. or lower.

＜＜Cooling process＞＞ The cooling process is a process of cooling the photosensitive resin composition layer at a cooling rate of 2°C/min or less after the heating process. The cooling rate of the cooling process is preferably 2°C/min or less, and more preferably 1°C/min or less. From the viewpoint of stress relaxation, the cooling rate of the cooling process is preferably 0.1°C/min or more. From the viewpoint of stress relaxation, it is better that the cooling rate of the cooling process is slower than that of the heating process.

The cooling process is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes. From the viewpoint of stress relaxation, in the method of manufacturing a laminate of the present invention, it is preferable that the time of the cooling process is longer than the time of the heating process.

The final temperature of the cooling process is preferably 30° C. or more lower than the glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing process. If the temperature is lowered by 30°C or more lower than the Tg of the photosensitive resin composition layer until the final reaching temperature of the cooling process, the polyimide will be sufficiently cured and the generation of interlayer delamination will be easily suppressed. The final temperature of the cooling process is preferably 160-250°C lower than the glass transition temperature of the photosensitive resin composition layer after the curing process, and particularly preferably 180-230°C lower.

<<Process set to room temperature>> After the photosensitive resin composition layer reaches the final temperature of the cooling process, it is preferable to cool the photosensitive resin composition layer at any temperature drop rate to set it to room temperature. The cooling rate of the process set to room temperature is not particularly limited, and it is better to be faster than the cooling rate of the cooling process. The temperature drop rate of the process set to room temperature can be set to, for example, 5 to 10°C/min.

<Metal layer formation process> The manufacturing method of the laminated body of the present invention includes a metal layer formation process of forming a metal layer on the surface of the photosensitive resin composition layer after the curing process by vapor phase film formation, and a curing process during the formation of the metal layer The temperature of the later photosensitive resin composition layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing process.

In the method for producing a laminate of the present invention, the temperature of the photosensitive resin composition layer when forming the metal layer is preferably 30°C or more lower than the glass transition temperature of the photosensitive resin composition layer, and more preferably 30 to 200°C lower Good, particularly good when the temperature is lower than 100～200℃. When the metal layer formed in the metal layer forming process is two or more layers, at least the metal layer (preferably a barrier metal film) directly in contact with the photosensitive resin composition layer after the curing process is formed. The temperature of the sexual resin composition layer is preferably in the above-mentioned range. When there are two or more metal layers formed in the metal layer forming process, the temperature of the photosensitive resin composition layer after the hardening process when forming the second metal layer is not particularly limited. However, even if it is the second metal layer, if there is a portion directly provided on the photosensitive resin composition layer, the temperature of the photosensitive resin composition layer after the curing process when forming the second metal layer is also in the above range For better. In particular, when vapor phase film formation is used to form the second metal layer, it is preferable that the temperature of the photosensitive resin composition layer after the curing process when forming the second metal layer is also within the above-mentioned range. In addition, when the second metal layer is formed by non-vapor phase film formation (electroplating, etc.), the temperature of the photosensitive resin composition layer after the curing process when the second metal layer is formed is generally lower than that of the photosensitive resin composition layer The temperature of the glass transition temperature.

The metal layer formed in the metal layer forming process is not particularly limited, and existing metals can be used. As the metal included in the metal layer formed in the metal layer forming process, copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, and tungsten, and compounds (including alloys) including at least one of them are exemplified. In the method for manufacturing the laminate of the present invention, the metal layer formed in the metal layer forming process preferably includes at least one of titanium, tantalum, and copper, and compounds including at least one of them, including titanium and copper, and including them At least one of the at least one compound is particularly preferred, and it is further particularly preferred to include copper. As a specific example when the metal layer contains at least one of titanium, tantalum, and copper, and a compound containing at least one of them, a metal layer including titanium, tantalum, copper, TiN, TaN, or TiW can be cited. , Copper, TiN or TiW metal layer is preferred. The metal contained in the metal layer formed in the metal layer forming process may be one type or two or more types.

In the manufacturing method of the laminated body of the present invention, the thickness of the metal layer formed in the metal layer forming process is preferably 50-2000 nm, more preferably 50-1000 nm, and particularly preferably 100-300 nm. In the manufacturing method of the laminate of the present invention, the metal layer formed in the metal layer forming process may be one layer or two or more layers. When the metal layer formed in the metal layer forming process is one layer, the metal layer is preferably used as the barrier metal film. When the metal layer formed in the metal layer forming process has two or more layers, the thickness of the entire metal layer formed in the metal layer forming process is preferably in the above-mentioned range. When the metal layer formed in the metal layer forming process is two or more layers, the metal layer formed in the metal layer forming process is preferably a laminate of a barrier metal film and a seed layer. The barrier metal film is preferably a layer that can shorten the penetration length of the metal into the cured film. Regarding the type of metal of the barrier metal film, the above-mentioned metal is preferable as the metal included in the metal layer formed in the metal layer forming process. The thickness of the barrier metal film is preferably from 50 to 2000 nm, more preferably from 50 to 1000 nm, and particularly preferably from 100 to 300 nm. The seed layer is preferably a layer for easily forming the pattern of the second metal layer formed in the second metal layer forming process. The metal of the seed layer is preferably the same metal as the second metal layer formed in the second metal layer forming process. The thickness of the seed layer is preferably from 50 to 2000 nm, more preferably from 50 to 1000 nm, and particularly preferably from 100 to 300 nm.

The method of forming the metal layer is not particularly limited, and an existing vapor phase film formation method can be applied. For example, sputtering method, chemical vapor deposition (chemical vapor deposition; CVD), plasma method, and a method of combining them can be considered. Among these, from the viewpoint of controlling the film thickness, the method of forming the metal layer is preferably a sputtering method.

<Second metal layer formation process> The manufacturing method of the laminate of the present invention further includes a second metal layer formation process of forming a second metal layer on the surface of the metal layer.

The second metal layer formed in the second metal layer forming process is not particularly limited, and existing metals can be used. Examples of metals included in the second metal layer formed in the second metal layer forming process include copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, and tungsten. From the viewpoint of using the laminate of the present invention as a rewiring layer of a semiconductor element, in the method of manufacturing the laminate of the present invention, it is preferable that the second metal layer contains copper.

In the manufacturing method of the laminate, the thickness of the second metal layer formed in the second metal layer forming process is, for example, 3-50 μm, preferably 3-10 μm, more preferably 5-10 μm, and particularly preferably 5-7 μm. When manufacturing a laminated body for power semiconductors, the thickness of the second metal layer formed in the second metal layer forming process is preferably 35-50 μm.

The method of forming the second metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, photolithography, lift-off, chemical vapor deposition (CVD), electrolytic plating, electroless plating, etching, printing, and a combination of them can be considered. More specifically, the patterning method by combining photolithography and etching, the patterning method by combining photolithography and electrolytic plating, the combined photolithography method, electroplating and etching patterns can be mentioned.化 method. As a patterning method that combines photolithography and electrolytic plating, after sputtering is used to form the seed layer of the metal layer formed in the metal layer formation process, the photolithography method is used to form the pattern of the seed layer, and the formation The method of electrolytic plating on the patterned seed layer to form the second metal layer is preferred. Then, etching may be further performed to remove the seed layer in the region where the second metal layer is not formed.

<Surface activation treatment process> The manufacturing method of the laminate may include a surface activation treatment process of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment process is usually performed after the metal layer formation process. After the curing process described above, the photosensitive resin composition layer may be subjected to a surface activation treatment process to form a metal 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 photosensitive resin composition layer after the curing process. Regarding both the metal layer and the photosensitive resin composition layer after the curing process , Can be performed separately for at least a part. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is more preferred to perform the surface activation treatment on a part or all of the area on which the photosensitive resin composition layer is further formed in the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion to the cured film provided on the surface can be improved. In addition, the surface activation treatment is preferably performed on part or all of the photosensitive resin composition layer (cured film) after the curing process. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, it is possible to improve the adhesion to the metal layer or the cured film provided on the surface that has been subjected to the surface activation treatment. When negative-tone development is performed, the exposed part is surface-treated, and the strength of the film is improved by curing or the like, so the photosensitive resin composition layer (cured film) is not damaged. As the surface activation treatment, specifically, plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, argon and oxygen mixed gas, etc.); corona discharge treatment; using CF ₄ and Etching treatment of O ₂ mixed gas, NF ₃ and O ₂ mixed gas, SF ₆ , NF ₃ and NF ₃ and O ₂ mixed gas; surface treatment using ultraviolet (ultraviolet; UV) ozone method; immersed in hydrochloric acid aqueous solution to remove oxidation After the coating, the organic surface treatment agent containing at least one of an amine group and a thiol group is dipped into an organic surface treatment agent; the mechanical roughening treatment using a brush is preferable. Plasma treatment is better, and oxygen plasma treatment using oxygen for the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is ^{preferably 500 to 200,000 J/m 2} , more preferably 1,000 to 100,000 J/m ^{2, and} even more preferably 10,000 to 50,000 J/m ² .

<Layering process> In the method of manufacturing a laminate of the present invention, after the metal layer forming process, the photosensitive resin composition layer forming process, the exposure process, the development process, the hardening process, and the metal layer forming process are further performed in sequence again For better. In this case, the metal layer forming process is repeatedly performed, and therefore, the effect of preventing interlayer peeling when the substrate, the cured film, and the metal layer are laminated is particularly effective. In this specification, after the metal layer forming process, the photosensitive resin composition layer forming process, the exposure process, the developing process, the hardening process, and the metal layer forming process are called the build-up process. The build-up process is preferably a process of forming a photosensitive resin composition layer, an exposure process, a developing process, a hardening process, a metal layer forming process, and a second metal layer forming process in sequence.

After the lamination process, when the lamination process is further performed, the surface activation treatment process can be further performed after the exposure process or the metal layer formation process. It is preferable to perform the above-mentioned layering process 3 to 7 times, and more preferably to perform 3 to 5 times. For example, like the cured film/metal layer/cured film/metal layer/cured film/metal layer, the cured film preferably has a structure of 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less. The more the multilayer structure is set, the more the photosensitive resin composition layer is repeatedly subjected to high-temperature processing in the developer or metal etching process and hardening process, so that it can suppress the metal layer/cured film caused by the manufacturing method of the laminate of the present invention. The effect of interlayer peeling occurs at the interface or the cured film/cured film interface. By adopting such a structure, a photosensitive resin composition layer (cured film) and a metal layer can be alternately laminated, and it can be used as a multilayer wiring structure of semiconductor elements such as a rewiring layer. Regarding the photosensitive resin composition layer (cured film), it is preferable that the thickness increases as the layer is stacked upward.

[Laminate] The laminate of the present invention has a substrate, a patterned cured film, and a metal layer on the surface of the patterned cured film. The patterned cured film contains polyimide or polybenzoxazole and constitutes the metal located on the surface of the patterned cured film. The penetration distance of the metal of the layer into the patterned cured film is 130 nm or less from the surface of the patterned cured film.

<Pattern cured film> It is preferable that the pattern cured film in the laminated body of this invention is the photosensitive resin composition layer after a hardening process in the manufacturing method of the laminated body of this invention.

＜＜Tg＞＞ The glass transition temperature of the pattern cured film (the photosensitive resin composition layer after the curing process) is preferably 150 to 300°C, more preferably 160 to 250°C, and particularly preferably 180 to 230°C.

＜＜Residual stress＞＞ The pattern cured film measured by the laser measurement method (the photosensitive resin composition layer after the curing process. The photosensitive resin composition layer after the metal layer formation process is preferred. The metal layer formation is more preferred. The residual stress of the photosensitive resin composition layer after the process and the second metal layer formation process is preferably less than 35 MPa, more preferably less than 25 MPa, and particularly preferably less than 15 MPa.

<Metal layer> The metal layer in the laminate of the present invention is preferably the metal layer formed in the metal layer forming process in the method of manufacturing the laminate of the present invention. In addition, the metal layer in the laminate of the present invention may be a laminate of the metal layer formed in the metal layer forming process in the method of manufacturing the laminate of the present invention and the second metal layer formed in the second metal layer forming process body. In this case, the metal layer formed in the metal layer forming process in the manufacturing method of the laminate of the present invention and the second metal layer formed in the second metal layer forming process are integrated to form the laminate of the present invention In the metal layer. In addition, the metal layer formed in the metal layer forming process in the manufacturing method of the laminate of the present invention is, for example, two layers of a barrier metal film and a seed layer. When the second metal layer formed in the second metal layer forming process is In the case of the same type of metal as the seed layer, only the seed layer and the second metal layer may be integrated. In this case, a laminate of only the layer in which the seed layer and the second metal layer are integrated, and the barrier metal film may be the metal layer in the laminate of the present invention. The thickness of the metal layer in the laminate of the present invention is preferably 0.1 to 50 μm at the thickest part, and more preferably 1 to 10 μm. From the viewpoint of stabilizing the film quality of the metal layer, the metal layer in the laminate of the present invention is preferably a flat metal layer. By using a sputtering method to form the metal layer, a flat metal layer can be formed. Furthermore, since the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing process, the metal layer is formed by sputtering. A more flat metal layer can be formed.

<The penetration length of the metal into the patterned hardened film> The penetration length of the metal forming the metal layer on the surface of the patterned hardened film into the patterned hardened film is 130nm or less from the surface of the patterned hardened film, preferably 50nm or less, more preferably 30nm or less .

[Method of Manufacturing Semiconductor Element] The method of manufacturing a semiconductor element of the present invention includes the method of manufacturing a laminate of the present invention. With the above configuration, the method for manufacturing a semiconductor element of the present invention provides a semiconductor element in which delamination between the substrate, the cured film, and the metal layer is suppressed when the substrate, the cured film, and the metal layer are laminated.

Hereinafter, an embodiment of a semiconductor element obtained by the method of manufacturing a semiconductor element of the present invention will be described. FIG. 1 is a schematic diagram showing the structure of an embodiment of a semiconductor element. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and the semiconductor wafer 101 in which a plurality of semiconductor wafers 101 a to 101 d are laminated is arranged on a wiring board 120. In addition, in this embodiment, the case where the number of layers of the semiconductor wafer is 4 is mainly described, but the number of layers of the semiconductor wafer is not particularly limited, and may be, for example, 2 layers, 8 layers, 16 layers, 32 layers, and the like. Also, it may be one layer.

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

The semiconductor wafer 101 has a structure in which a semiconductor wafer 101a having no through electrodes and a semiconductor wafer 101b to 101d having through electrodes 102b to 102d are flip-chip bonded. That is, the electrode pads of the semiconductor wafer 101a without through electrodes and the bonding pads on the semiconductor wafer 101a side of the semiconductor wafer 101b with through electrodes 102b adjacent thereto are connected by metal bumps 103a such as solder bumps. The connection pad on the other side of the semiconductor chip 101b with the through electrode 102b and the connection pad on the semiconductor chip 101b side of the semiconductor chip 101c with the through electrode 102c adjacent to it are connected by metal bumps 103b such as solder bumps. . Similarly, the connection pad on the other side of the semiconductor chip 101c with the through electrode 102c and the connection pad on the semiconductor chip 101c side of the semiconductor chip 101d with the through electrode 102d adjacent to it are made of metal bumps such as solder bumps. 103c and connected.

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

The semiconductor wafer 101 is arranged on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring substrate in which an insulating substrate such as a resin substrate, a ceramic substrate, and a peeling substrate is used as a base material is used. As the wiring board 120 to which the resin substrate is applied, a multilayer copper laminate (multilayer printed wiring board) or the like can be cited.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. An insulating layer 115 in which a rewiring layer 105 is formed is arranged between the wiring substrate 120 and the semiconductor wafer 101, and the wiring substrate 120 and the semiconductor wafer 101 are electrically connected via the rewiring layer 105. As the insulating layer 115, the photosensitive resin composition layer (cured film) after the curing process in the present invention can be used. As the insulating layer 115 on which the rewiring layer 105 is formed, a laminate obtained by the method of manufacturing a laminate of the present invention can be used. One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor wafer 101d on the side of the rewiring layer 105 via a metal bump 103d such as a solder bump. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Furthermore, an underfill layer 110a is formed between the insulating layer 115 and the semiconductor wafer 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

Fig. 2 is a schematic diagram showing the structure of an embodiment of a laminate obtained by the method of manufacturing a laminate of the present invention. Specifically, FIG. 2 shows an example of using the laminate obtained by the method of manufacturing the laminate of the present invention as a rewiring layer. In FIG. 2, 200 denotes a laminate obtained by the method of the present invention, 201 denotes a photosensitive resin composition layer (cured film), and 203 denotes a metal layer. In FIG. 2, the metal layer 203 is a layer indicated by diagonal lines. The photosensitive resin composition layer 201 is formed in a desired pattern by negative-tone development. The metal layer 203 is formed so as to cover a part of the surface of the aforementioned pattern, and a photosensitive resin composition layer (cured film) 201 is further laminated on the surface of the aforementioned metal layer 203. Furthermore, the photosensitive resin composition layer (cured film) functions as an insulating layer, and the metal layer functions as a rewiring layer, and is mounted on the above-mentioned semiconductor element as a rewiring layer. [Example]

The following examples are given to illustrate the present invention in more detail. The materials, usage amount, ratio, processing content, and processing flow shown in the following embodiments are within the scope of the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" within the range without special instructions are quality standards.

[Example 1] ＜Synthesis of polyimide precursor＞ ＜＜From 4,4'-oxodiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-methacrylic acid Synthesis of the polyimine precursor Aa-1 (polyimine precursor with radical polymerizable group) of hydroxyethyl ester>> 20.0g (64.5 millimoles) of 4,4'-oxodi Phthalic dianhydride (obtained by drying 4,4'-oxodiphthalic acid at 140°C for 12 hours), 18.6 g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diglyme) were mixed. The mixture was stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. After the reaction mixture was diluted with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 millimoles) of 4,4'-oxodiphenylamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23° C. for 20 minutes. Then, the reaction mixture was stirred at room temperature for one night. Next, the reaction mixture was added to 5 liters of water to precipitate the polyimide precursor. The mixture of water and polyimide precursor was stirred at a speed of 5000 rpm for 15 minutes. The mixture of water and the polyimide precursor was filtered to remove the filtrate, and the residue containing the polyimide precursor was added to 4 liters of water. The mixture of water and the polyimide precursor was again stirred for 30 minutes, and filtered again to obtain a polyimide precursor as a residue. Next, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain the polyimide precursor Aa-1. The structure of the polyimide precursor Aa-1 is shown below. [Chemical formula 49] Aa-1

<Preparation of photosensitive resin composition> The following components were mixed, and the photosensitive resin composition was prepared as a uniform solution.

<<Composition of photosensitive resin composition A-1>> Resin: polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass photopolymerization initiator C-1 1.0 parts by mass Polymerization inhibitor: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.08 parts by mass migration inhibitor: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.12 parts by mass Metal adhesion modifier: N -[3-(Triethoxysilyl)propyl]maleic acid monoamide 0.70 parts by mass Solvent: 48.00 parts by mass γ-butyrolactone Solvent: 12.00 parts by mass dimethylsulfene

<<Composition of photosensitive resin composition A-2>> Resin: polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass photopolymerization initiator C-1 1.0 parts by mass Polymerization inhibitor: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass migration inhibitor: 1H-1,2,4-triazole (Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass solvent: 48.00 parts by mass γ-butyrolactone solvent: 12.00 parts by mass dimethylsulfoxide

The details of each additive are as follows. B-1: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure) [Chemical formula 50]

(C) Photopolymerization initiator C-1: Compound 24 described in paragraph 0345 of JP 2014-500852 A [Chemical formula 51]

<Filtering process> Each photosensitive resin composition was filtered under pressure by passing through a filter having a pore width of 0.8 μm.

<Photosensitive resin composition layer formation process> Then, each photosensitive resin composition was applied to a silicon wafer by a spin coating method to form a layer, thereby forming a photosensitive resin composition layer.

<Drying process> The silicon wafer with the obtained photosensitive resin composition layer was dried on a hot plate at 100°C for 5 minutes to obtain a uniform photosensitive resin with a thickness of 20μm on the silicon wafer Composition layer.

<Exposure process> Next, a stepper (Nikon NSR 2005 i9C) was used to expose the photosensitive resin composition layer on the silicon wafer ^{with an exposure wavelength of 365nm (i-ray) and an exposure energy of 500mJ/cm 2} (Full and uniform irradiation). In this embodiment, in order to easily measure the stress, the exposure is performed under uniform irradiation on the entire surface, immersed in a developer solution, and undergoes a curing process to form a cured film. However, it is also possible to perform pattern exposure, immerse in a developer solution to remove unexposed parts, and go through a curing process to form a patterned cured film. Compared with the unpatterned case, when the photosensitive resin composition layer is patterned, more interfaces are generated, and the contact area between the layers when the substrate, the cured film and the metal layer are laminated is less. . In this case, delamination becomes easier to occur, and the effect of the present invention is more clearly obtained.

<Development process> The photosensitive resin composition layer which has been fully exposed was immersed in cyclopentanone for 60 seconds, and the development process was performed.

<Curing process> Next, the photosensitive resin composition layer after the development process was cured using the following methods (1) to (4).

＜＜(1) Heating process＞＞ First, in a nitrogen environment with an oxygen concentration of 20 vol ppm or less, the substrate with the photosensitive resin composition layer after the development treatment is placed on a plate that can adjust the temperature from room temperature ( 20°C) The temperature is increased at a temperature increase rate of 10°C/min, and the temperature is finally reached to 230°C in 21 minutes.

<<(2) Holding process>> Then, the photosensitive resin composition layer was maintained at 230° C., which is the final temperature (holding temperature) of the heating process, for 3 hours.

＜＜(3) Cooling process＞＞ The photosensitive resin composition layer heated for 3 hours in the holding process is slowly cooled from 230°C at a temperature drop rate of 2°C/min over 30 minutes to the final temperature of the cooling process 170°C .

＜＜(4) Process set to room temperature＞＞ After the photosensitive resin composition layer reaches the final temperature of 170°C in the cooling process, the photosensitive resin composition layer is cooled at a temperature drop rate of 5-10°C/min. It was set to room temperature, and a cured film was obtained.

<Metal layer formation process> Next, in a sputtering device (manufactured by AMAT, product name Endura), a first metal layer is formed on the photosensitive resin composition layer after the curing process, and the first metal layer is sputtered Under the condition that the temperature of the photosensitive resin composition layer becomes 150°C, Ti is formed into a 100nm film to serve as a barrier metal film, and Cu is continuously formed into a 300nm film to form a second metal layer serving as a seed layer . The thickness of the entire metal layer formed in the metal layer forming process using the sputtering method is set to 400 nm. In the sputtering device, the temperature of the photosensitive resin composition layer is measured and obtained by attaching a sealing material (thermal label, NiGK Corporation) that changes color according to the temperature to the surface and observing the change in color. The temperature of the surface of the layer.

<Second metal layer formation process> Next, a dry film resist (manufactured by Hitachi Chemical Co., Ltd., product name Photec RY-3525) is applied to the seed layer by roll lamination to form a patterned coating The film machine was bonded and exposed with an EXM-1201 exposure machine manufactured by ORC MANUFACTURING CO., LTD. with an energy of ^{100mJ/cm 2.} Next, spray development was performed for 90 seconds with a 1% by mass sodium carbonate aqueous solution at 30° C. to open the dry film resist. Next, an electrolytic copper plating method was used to form a copper plating layer with a thickness of 7 μm on the dry film resist and on the seed layer of the part where the dry film resist opened. Next, the dry film resist was peeled off using a peeling liquid. Then, an etching solution was used to remove the seed layer (300 nm Cu layer) of the part where the dry film resist was stripped, and a patterned metal layer was formed on the surface of the photosensitive resin composition layer after the curing process.

<Characteristics of Cured Film> <<Measurement of Glass Transition Temperature>> About the photosensitive resin composition layer (cured film) after the curing process, the glass transition temperature was measured using the following method. A dynamic viscoelasticity measuring device was installed, and the Tg was determined from the peak temperature of tanδ by heating from 0°C to 350°C at a frequency of 1 Hz and a heating rate of 10°C/min using the stretching method. The obtained results are described in Table 1 below.

<<Measurement of stress>> Regarding the photosensitive resin composition layer (cured film) after the metal layer formation process and the second metal layer formation process, the stress was measured using the following method. Regarding the silicon wafer before the coating of the photosensitive resin composition layer, the wafer was mounted on a thin film stress measuring device, and a laser scan was performed at room temperature to obtain a blank value. Mount the wafer with the photosensitive resin composition layer (cured film) formed after the metal layer formation process and the second metal layer formation process in the thin film stress measuring device, and after laser scanning at room temperature, it is combined with the photosensitive resin The blank value before coating of the object layer was compared, and the stress was measured according to the film thickness and the radius of curvature. The obtained results are described in Table 1 below.

<Laminating process> Furthermore, for the surface with unevenness formed by the metal layer and the photosensitive resin composition layer after the curing process, the same photosensitive resin composition is used again, and the photosensitive resin composition is implemented again in the same manner as above. From the filtration process to the curing process of the substance, a laminate with two layers of the photosensitive resin composition after the curing process is formed. Furthermore, the laminated body having the photosensitive resin composition layer after the two-layer hardening process was subjected to the metal layer forming process and the second metal layer forming process again in the same manner as described above to form a laminated body.

<Evaluation of the laminate> <<Measurement of the penetration length of the metal into the cured film>> Regarding the laminate after the metal layer formation process and the second metal layer formation process, use the following method to apply the following method to the metal layer formation process using the sputtering method The penetration length of the metal to the cured film was measured. Through the focused ion beam (Focused Ion Beam; FIB) and transmission electron microscope (TEM) to directly observe the profile to determine its length, and at the same time using a high-angle scattering dark-field scanning transmission electron microscope (high-angle annular dark- Field scanning transmission electron microscopy; HAADF-STEM) and electron energy loss spectroscopy (Electron Energy Loss Spectroscopy; EELS) were analyzed. The obtained results are described in Table 1 below.

<<Peel test after cycle test>> The layered body after the lamination process was subjected to a peel test after the cycle test using the following method. After cooling each layered body at -55°C in nitrogen for 30 minutes, 500 cycles were performed in a cycle of heating at 125°C for 30 minutes. Then, each laminate was cut out in a direction perpendicular to the surface of the cured film to have a width of 5 mm, and the part where the cured film and the metal layer were in contact and the part where the metal layer and the second metal layer were in contact were cut out, and observed It was cross-sectioned and confirmed with an optical microscope whether one slice was peeled between the cured film and the metal layer and between the metal layer and the second metal layer. "No peeling" is preferable. The obtained results are described in Table 1 below.

[Examples 2 to 6 and Comparative Examples 1 to 3] Except for changing the conditions shown in the following table, in the same manner as in Example 1, Examples 2 to 6 and Comparative Examples 1 to 3 were produced Layered body. In the same manner as in Example 1, the measurement of the characteristics of the cured film and the evaluation of the laminate were performed.

[Table 1]

From Table 1 above, it can be seen that when the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing process, the residual stress of the cured film is lower It is small and can provide a laminate with a short metal penetration length after the metal layer formation process using the sputtering method. It is understood that in the laminate of the present invention in which the residual stress of the cured film is small and the penetration length of the metal is short, it is possible to suppress delamination when the substrate, the cured film, and the metal layer are laminated. On the other hand, according to Comparative Examples 1 to 3, when the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is higher than the glass transition temperature of the photosensitive resin composition layer after the curing process, the cured film The residual stress is large, and a laminate with a long metal penetration length after the metal layer formation process using the sputtering method is obtained. It was found that in the laminates of Comparative Examples 1 to 3 in which the residual stress of the cured film was large and the penetration length of the metal was long, delamination occurred when the substrate, the cured film, and the metal layer were laminated.

In Example 1, the metal layer (copper thin film) was changed to an aluminum thin film, and it was performed in the same manner as the other methods. As a result, the same good results as in Example 1 were obtained. In Example 1, the composition ratio of the solid content concentration of the photosensitive resin composition 1 was set to 1/10 without changing the composition ratio, and spraying was performed using a spray gun ("NanoSpray" made by EV Group, ALL, Australia). The laminated body was formed in the same manner as in Example 1. The same excellent effect as in Example 1 was obtained. In the production of the laminate of Example 1, before heating at 230°C for 3 hours, heating (pretreatment) at 100°C for 10 minutes, except that the laminate was produced in the same manner as in Example 1, and The characteristics were evaluated. The same excellent effect as in Example 1 was obtained. In the production of the laminate of Example 1, before heating at 230°C for 3 hours, heating (pretreatment) at 150°C for 10 minutes, except that the laminate was produced in the same manner as in Example 1, and The characteristics were evaluated. The same excellent effect as in Example 1 was obtained. In the production of the laminated body of Example 1, the laminated body was produced in the same manner as in Example 1, except that UV light was irradiated at 230°C for 3 hours before heating (pretreatment) at 180°C for 10 minutes. , And evaluated its characteristics. The same excellent effect as in Example 1 was obtained. [Industrial availability]

In the laminate produced by the method of producing the laminate of the present invention, it is possible to suppress delamination when the substrate, the cured film, and the metal layer are laminated. Furthermore, in the laminated body manufactured by the manufacturing method of the laminated body of this invention, even when the laminated body which laminated|stacked two or more sets of a board|substrate, a cured film, and a metal layer, peeling between layers can be suppressed. Such a laminate can be used as an interlayer insulating layer for a rewiring layer for manufacturing semiconductor elements, and can provide an interlayer insulating layer for a rewiring layer in which delamination is suppressed. In addition, this type of laminate can be used as an interlayer insulating layer for the manufacture of power semiconductors, a copper pillar intermediate film for three-dimensional IC (Three-Dimensional Integrated Circuit), a single-layer insulating layer, and an interlayer insulating layer for panel applications.

100‧‧‧Semiconductor element 101, 101a～101d‧‧‧Semiconductor chip 102b, 102c, 102d‧‧‧ Through electrode 103a～103e‧‧‧Metal bump 105‧‧‧Rewiring layer 110, 110a, 110b‧‧‧ Underfill layer 115‧‧‧Insulation layer 120‧‧‧Wiring substrate 120a‧‧‧Surface electrode 200‧‧‧Laminate 201‧‧‧Photosensitive resin composition layer (hardened film) 203‧‧‧Metal layer

100: Semiconductor components

101, 101a~101d: semiconductor wafer

102b, 102c, 102d: through electrode

103a~103e: Metal bump

105: redistribution layer

110, 110a, 110b: underfill layer

115: insulating layer

120: Wiring board

120a: Surface electrode

Claims (12)

A method for manufacturing a laminated body includes the following processes in sequence: a photosensitive resin composition layer forming process, applying the photosensitive resin composition to a substrate to form a layer; an exposure process corresponding to the photosensitive resin composition used for the aforementioned substrate The photosensitive resin composition layer is exposed; the development process is to develop the exposed photosensitive resin composition layer; the curing process is to harden the developed photosensitive resin composition layer; and the metal layer formation process, A metal layer is formed on the surface of the photosensitive resin composition layer after the curing process by vapor phase film formation; and the temperature of the photosensitive resin composition layer after the curing process when the metal layer is formed is lower than the curing process The glass transition temperature of the photosensitive resin composition layer after the process. The curing process includes a temperature-rising process of raising the temperature of the photosensitive resin composition layer and maintaining a holding temperature equal to the final temperature of the aforementioned temperature-rising process. The holding process, the holding temperature in the holding process is 250° C. or lower. The manufacturing method of the laminated body as described in the first item of the patent application, which further includes the aforementioned photosensitive resin composition layer forming process, the aforementioned exposure process, the aforementioned development treatment process, the aforementioned curing process, and the aforementioned metal layer which are carried out in sequence again Formation process. The method for manufacturing a laminate as described in claim 1 or 2, wherein the photosensitive resin composition constructs a cross-linked structure by exposure to reduce solubility in organic solvents. The method of manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application, wherein The aforementioned photosensitive resin composition includes at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. The method for manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application further includes a second metal layer forming process to form a second metal layer on the surface of the metal layer. The method for manufacturing a laminate as described in claim 5, wherein the second metal layer includes copper. According to the method for manufacturing a laminate as described in item 1 or item 2, the aforementioned metal layer includes at least one of the following compounds, and the compound includes at least one of titanium, tantalum, and copper. According to the method for manufacturing a laminated body described in item 1 or item 2 of the scope of the patent application, the thickness of the metal layer formed in the metal layer forming process is 50 to 2000 nm. The method for manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application, wherein the residual stress of the photosensitive resin composition after the curing process measured according to the laser measurement method is less than 35 MPa. The method for producing a laminate as described in the first or second patent application, wherein the photosensitive resin composition is a photosensitive resin composition for negative development. The method for manufacturing a laminate as described in item 1 or item 2 of the scope of the patent application, wherein the temperature of the photosensitive resin composition layer when the metal layer is formed is lower than the glass transition temperature of the photosensitive resin composition layer Above 30°C. A method for manufacturing a semiconductor element includes the method for manufacturing a laminated body as described in any one of items 1 to 11 in the scope of the patent application.

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