JP6650517B2 - Method for producing cured film, method for producing laminate, and method for producing semiconductor element - Google Patents

Description

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

BACKGROUND ART High heat-resistant resins such as a polyimide resin and a polybenzoxazole resin have excellent heat resistance and insulating properties, and are therefore used for insulating layers of semiconductor elements.
In addition, a high heat-resistant resin such as a polyimide resin or a polybenzoxazole resin is used in the state of a precursor (a polyimide precursor or a polybenzoxazole precursor) before the cyclization reaction. In some cases, a precursor is cyclized to produce a cured film.
For example, in a method of manufacturing a cured film using general heat of a polyimide resin, the resin is heated, kept at a constant temperature, and then cooled.
Regarding the heating process, multi-stage heating has been proposed to improve the pattern shape (Patent Document 1).
Regarding the cooling step, a method is known in which the temperature is reduced at a rate of about 3 to 5 ° C./min in consideration of the processing time (Patent Document 2).

JP 2015-187676 A US Patent No. 9159547

However, it has been found that the conventional method of producing a cured film using heat has a problem that the substrate is easily warped.
Further, it has been found that when a cured film and a metal layer are laminated in order to use the cured film as an interlayer insulating layer for a rewiring layer of a semiconductor element, there is a problem that delamination occurs. Specifically, it was found that the adhesion between the cured film and the metal layer was insufficient. Furthermore, it was found that when two or more laminates of the cured film and the metal layer were combined, the adhesion between the cured films was insufficient.
The problem to be solved by the present invention is to provide a method of manufacturing a cured film capable of suppressing the warpage of a substrate when the substrate and the cured film are stacked. It is another object of the present invention to provide a method for manufacturing a laminated body and a method for manufacturing a semiconductor element, which can suppress delamination when a substrate, a cured film, and a metal layer are stacked.

In order to solve the above-mentioned problems, the present inventors conducted a study, and from the results of the analysis of the internal stress, under the conventional temperature-lowering condition, when the substrate warped from the internal stress due to the temperature fluctuation, and when the metal layer was further laminated, It was found to cause delamination.
It has conventionally been considered that lowering the cooling rate increases the time required for the process, which is not desirable from the viewpoint of productivity. FIGS. 1A and 1B of Patent Document 2 show an example of a cooling rate of 3.2 ° C./min and 2.2 ° C./min, but Patent Document 2 does not show the reason for changing the cooling rate. Was.
Under such circumstances, the present inventors set the temperature drop rate to 2 ° C./min or less when manufacturing a cured film using a high heat resistant resin such as a polyimide resin or a polybenzoxazole resin. The inventors have found that the above problems can be solved, and have completed the present invention.
According to the evaluations of the present inventors, the temperature lowering conditions of Patent Document 2 are not sufficient to suppress the warpage of the substrate when the substrate and the cured film are laminated and the delamination when the metal layer is further laminated. Was.

The present invention, which is a means for solving the above problems, and preferred embodiments of the present invention are as follows.
[1] a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer;
An exposure step of exposing the photosensitive resin composition layer,
A developing process of performing a developing process on the exposed photosensitive resin composition layer,
A curing step of curing the photosensitive resin composition layer after the development processing,
In the above order,
The curing process
A temperature raising step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature,
A cooling step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.
[2] The method for producing a cured film according to [1], further comprising a holding step of holding the holding temperature equal to the final temperature of the heating step for at least 30 minutes after the heating step and before the cooling step.
[3] The method for producing a cured film according to [2], wherein the holding temperature in the holding step is 150 to 450 ° C.
[4] The method for producing a cured film according to any one of [1] to [3], wherein the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor.
[5] The method for producing a cured film according to any one of [1] to [4], wherein the time of the cooling step is longer than the time of the temperature raising step.
[6] The method for producing a cured film according to any one of [1] to [5], wherein the final temperature of the cooling step is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
[7] The method for producing a cured film according to any one of [1] to [6], wherein a residual stress of the photosensitive resin composition layer after the curing step, measured according to a laser measurement method, is less than 35 MPa.
[8] The method for producing a cured film according to any one of [1] to [7], wherein the photosensitive resin composition is for negative-tone development.
[9] The method for producing a laminate according to any one of [1] to [8], wherein the photosensitive resin composition forms a crosslinked structure upon exposure to light and decreases the solubility in an organic solvent.
[10] The method for producing a cured film according to any one of [1] to [9],
A method for producing a laminate, further comprising a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step.
[11] The method for producing a laminate according to [10], wherein the photosensitive resin composition layer forming step, the exposing step, the developing step, and the curing step are performed again in the above order.
[12] The method according to [10] or [11], wherein the photosensitive resin composition layer forming step, the exposing step, the developing step, the curing step, the heating step, the cooling step, and the metal layer forming step are performed again in the above order. A method for manufacturing a laminate.
[13] A method for manufacturing a semiconductor device, including the method for manufacturing a laminate according to any one of [10] to [12].

[14] A cured film obtained by the method for producing a cured film according to any one of [1] to [9].
[15] A laminate obtained by the method for producing a laminate according to any one of [10] to [12].
[16] A semiconductor device obtained by the method for manufacturing a semiconductor device according to [13].

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hardened film which can suppress the curvature of a board | substrate when a board | substrate and a hardened film are laminated can be provided. Further, according to the present invention, it is possible to provide a method of manufacturing a laminate and a method of manufacturing a semiconductor element, which can suppress delamination when a substrate, a cured film, and a metal layer are stacked.

FIG. 2 is a schematic view illustrating a configuration of an embodiment of a semiconductor device. It is the schematic which shows the structure of one Embodiment of the laminated body obtained by the manufacturing method of the laminated body of this invention.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, “(meth) acrylate” represents both or “acrylate” and “methacrylate”, and “(meth) allyl” represents both “allyl” and “methallyl”, or Represents either, “(meth) acryl” represents both “acryl” and “methacryl” or either, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Indicates one of them.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present specification, the solid content concentration is a mass percentage of the other components except for the solvent with respect to the total mass of the composition. The solid content concentration means a concentration at 25 ° C. unless otherwise specified.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values by gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, and TSKgel as columns. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). The eluent was measured using THF (tetrahydrofuran) unless otherwise specified. Unless otherwise stated, detection is performed using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).

[Method of manufacturing cured film]
The method for producing a cured film of the present invention comprises applying a photosensitive resin composition to a substrate to form a layer, a photosensitive resin composition layer forming step,
An exposure step of exposing the photosensitive resin composition layer,
A developing process of performing a developing process on the exposed photosensitive resin composition layer,
A curing step of curing the photosensitive resin composition layer after the development processing,
In the above order,
The curing process
A temperature raising step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature,
A cooling step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.
With the above configuration, the method for producing a cured film of the present invention can suppress the warpage of the substrate when the substrate and the cured film are laminated. It is presumed that by lowering the cooling rate after the temperature raising step and cooling, the residual stress inside the cured film can be reduced, and as a result, the warpage of the substrate when the substrate and the cured film are laminated can be suppressed. Is done.
Hereinafter, preferred embodiments of the present invention will be described in detail.

<Filtration process>
The method for producing a cured film of the present invention may include a step of filtering the photosensitive resin composition before applying the photosensitive resin composition to a substrate. Filtration is preferably performed using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore sizes and / or materials may be used in combination. Further, filtration may be performed a plurality of times using each type of material, and the step of performing the filtration a plurality of times may be a circulation filtration step. Pressure filtration may be performed, and the pressure applied in the case of pressure filtration is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, filtration using an adsorbent may be performed to remove impurities, or filtration may be performed using a combination of filter filtration and an adsorbent. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.

<Photosensitive resin composition layer forming step>
The method for producing a cured film of the present invention includes a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer.
As a means for applying the photosensitive resin composition to the substrate, coating is preferable.
Specifically, as means to be applied, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, slit coating, And an ink-jet method. 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. A desired photosensitive resin composition layer can be obtained by adjusting the appropriate solid content concentration and application conditions according to the means to be applied. The coating method can also be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, or an inkjet method is preferable. For a rectangular substrate, a slit coating method, a spray coating method, or an inkjet method is used. Method is preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm (revolutions per minute) for about 10 seconds to 1 minute.
The thickness of the photosensitive resin composition layer (the cured film after the curing step) is preferably applied to be 0.1 to 100 μm after exposure, and is preferably applied to be 1 to 50 μm. More preferred. Further, as shown in FIG. 2, the thickness of the formed photosensitive resin composition layer is not necessarily required to be uniform. In particular, when a photosensitive resin composition layer is provided on an uneven surface, cured films having different thicknesses will be obtained as shown in FIG. In particular, when a plurality of cured films are laminated, a concave portion having a large depth may be formed as the concave portion. However, the technical value of the present invention is such that the delamination between layers can be more effectively suppressed. high. When the laminate has cured films having different thicknesses, the thickness of the cured film in the thinnest portion is preferably the above-described thickness.

<< Substrate >>
The type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, an optical film, a ceramic material, a deposited film, and a magnetic film , A reflective film, a metal substrate of Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, and an electrode plate of a plasma display panel (PDP). In the present invention, a semiconductor fabrication substrate is particularly preferred, and silicon is more preferred.
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 may be used as a substrate.

<< photosensitive resin composition >>
Hereinafter, the details of the photosensitive resin composition used in the present invention will be described.
In the method for producing a cured film of the present invention, it is preferable to include a compound that forms a crosslinked structure by exposure, more preferably the photosensitive resin composition is for negative-tone development, and the crosslinked structure is constructed by exposure to an organic compound. It is particularly preferable that the solubility in a solvent is reduced, and it is most preferable that the negative photosensitive resin is developed with an organic solvent.
First, components that may be included in the photosensitive resin composition used in the present invention will be described. The photosensitive resin composition may contain components other than these, and these components are not essential.

<<<< 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 high heat resistant resin.

  The photosensitive resin composition used in the present invention preferably contains, as a resin, a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. In the method for producing a cured film of the present invention, the photosensitive resin composition preferably contains a polyimide precursor or a polybenzoxazole precursor, and more preferably contains a polyimide precursor.

The photosensitive resin composition used in the present invention may contain only one kind of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, or may contain two or more kinds. Further, two or more kinds of resins of the same kind, such as two kinds of polyimide precursors, having different structures may be included.
The content of the resin in the photosensitive resin composition used in the present invention is preferably from 10 to 99% by mass, more preferably from 50 to 98% by mass, and more preferably from 70 to 96% by mass of the total solids of the photosensitive resin composition. More preferred.

Further, the resin preferably contains a polymerizable group.
Further, the photosensitive resin composition preferably contains a polymerizable compound. With such a configuration, a three-dimensional network is formed in the exposed area, and a strong crosslinked film is formed. The adhesion treatment more effectively improves the adhesion between the cured film and the metal layer or the adhesion between the cured films.
Furthermore, the resin preferably includes a partial structure represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- , -SO ₂ - or -NHCO-, and a group of two or more combinations of the above. With such a configuration, the photosensitive resin composition layer (cured film) has a flexible structure, and the effect of suppressing the occurrence of delamination is more effectively exhibited. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group of fluorine carbon atoms which may be substituted with atoms 1 or 2, -O -, - CO - , - S- or -SO ₂ - and more preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（２）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。(Polyimide precursor)
The type and the like of the polyimide precursor are not particularly limited, and it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
Equation (2)

During 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, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² in the formula (2) are preferably an oxygen atom or NH, and more preferably an oxygen atom.
R ¹¹¹ in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, A cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group including an aromatic group having 2 to 60 carbon atoms is more preferable. As a particularly preferred embodiment, it is exemplified that R ¹¹¹ in the formula (2) is a group represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- , -SO ₂ - or -NHCO-, and a group of two or more combinations of the above. These preferred ranges are as described above.

Preferably, R ¹¹¹ in formula (2) is derived from a diamine. Examples of the diamine used for producing the polyimide precursor include a linear or branched aliphatic, cyclic aliphatic or aromatic diamine. One type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof And more preferably a diamine containing a group consisting of an aromatic group having 2 to 60 carbon atoms. Examples of the aromatic group include the following aromatic groups.

上記芳香族基中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ（＝Ｏ）₂−、−ＮＨＣＯ−ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−ＳＯ₂−から選択される基であることがより好ましく、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、および、−Ｃ（ＣＨ₃）₂−からなる群から選択される２価の基であることがさらに好ましい。

In the above aromatic group, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C (= O)-, -S- , —S (＝ O) ₂ —, —NHCO— and a group selected from the combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O -, - C (= O ) -, - S -, - SO 2 - , more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, More preferably, it is a divalent group selected from the group consisting of —C (CF ₃ ) ₂ — and —C (CH ₃ ) ₂ —.

  Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- 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-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4′-diaminopara Terphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- ( 2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenyl sulfone 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4 4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl Hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ′, 4,4′-tetraaminobiphenyl, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9 -Bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4 -And 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, 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-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoro Propane, parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4′-bis (4-amido No-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl Sulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, , 3 ', 5,5'-Tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (tri Fluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotridene and 4,4 ′ ″-diaminoquaterphenyi At least one diamine selected from the like.

  Further, the following diamines (DA-1) to (DA-18) are also preferable.

Diamines having at least two or more alkylene glycol units in the main chain are also preferred examples. Preferably, it is a diamine containing two or more ethylene glycol chains and / or propylene glycol chains in one molecule, and more preferably a diamine containing no aromatic ring. As specific examples, 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 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- ( Examples include, but are not limited to, 2-aminopropoxy) ethoxy) propoxy) propan-2-amine.
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, The structure of Jeffamine® EDR-176 is shown below.

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

R ¹¹¹ in the formula (2) is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the obtained cured film. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- , -SO ₂ - or -NHCO-, and a group of two or more combinations of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group of fluorine carbon atoms which may be substituted with atoms 1 or 2, -O -, - CO - , - S- or -SO ₂ - and more preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（５１）中、Ｒ¹⁰〜Ｒ¹⁷は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ¹⁰〜Ｒ¹⁷の少なくとも１つはフッ素原子、メチル基またはトリフルオロメチル基である。
Ｒ¹⁰〜Ｒ¹⁷の１価の有機基として、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。
式（６１）

式（６１）中、Ｒ¹⁸およびＲ¹⁹は、それぞれ独立にフッ素原子またはトリフルオロメチル基である。
式（５１）または（６１）の構造を与えるジアミン化合物としては、２，２’−ジメチルベンジジン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種類を用いるか、または２種類以上を組み合わせて用いてもよい。R ¹¹¹ in the formula (2) is preferably a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-line transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-line transmittance and availability.
Equation (51)

In the 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. It is.
As the monovalent organic group represented by R ^{10 to} R ¹⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) or a fluorocarbon having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
Equation (61)

In the formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and 2,2′- Bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.

式（５）中、Ｒ¹¹²は、単結合、または、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ₂−、−ＮＨＣＯ−ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−ＣＯ−、−Ｓ−および−ＳＯ₂−から選択される基であることがより好ましく、−ＣＨ₂−、−Ｃ（ＣＦ₃）₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、−ＣＯ−、−Ｓ−および−ＳＯ₂−からなる群から選択される２価の基がさらに好ましい。R ¹¹⁵ in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
Equation (5)

In the formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, —O—, —CO—, —S—, —SO _2- , -NHCO-, and a group selected from these combinations are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO- , -S- and -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - C (} CF 3) 2 -, - C (CH 3) 2 -, - O -, - CO -, - S- and -SO ₂ - 2 divalent radical selected from the group consisting of is more preferable.

Equation (6)

式（Ｏ）中、Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵の好ましい範囲は式（２）におけるＲ¹¹⁵と同義であり、好ましい範囲も同様である。Specific examples of R ¹¹⁵ in the formula (2) include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride. One kind of tetracarboxylic dianhydride may be used alone, or two or more kinds may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Formula (O)

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

  Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic acid Acid dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic 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-naphthalene Te Lacarboxylic 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 Acid dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxy Nyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and those having 1 to 1 carbon atoms Examples include at least one selected from 6 alkyl and / or C1 to C6 alkoxy derivatives.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ in formula (2) has a hydroxy group. More specifically, R ¹¹¹ is a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ in the 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 preferably contain a polymerizable group. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, a radical, or the like. As the polymerizable group, a photo-radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group. Is mentioned. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
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.
Examples of suitable R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene. _{, -CH 2 CH (OH) CH} 2 - and the like, ethylene group, propylene group, trimethylene _{group, -CH 2 CH (OH) CH} 2 - is more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

R ¹¹³ or R ¹¹⁴ in the formula (2) may be a monovalent organic group other than a polymerizable group.
From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ in the formula (2) is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group. Examples of the monovalent organic group include an aromatic group having one, two, or three (preferably one) acidic groups bonded to the carbon constituting the aryl group, and a carbon bonded to the carbon constituting the aryl group. An aralkyl group having one, two or three (preferably one) acidic groups is particularly preferred. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably a hydroxy group.
More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

The alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) preferably has 1 to 30 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
The cyclic alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) may be a monocyclic alkyl group or a polycyclic alkyl group. Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alkyl group include, for example, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Above all, a cyclohexyl group is most preferred from the viewpoint of compatibility with high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.
As the aromatic group represented by R ¹¹³ or R ¹¹⁴ in the formula (2), specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene Ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring Phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or a phenazine ring. A benzene ring is most preferred.

When R ¹¹³ in the formula (2) is a hydrogen atom, or when R ¹¹⁴ in the formula (2) is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. It may be. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

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

  In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the polyimide precursor. Specifically, as a diamine component for introducing an aliphatic group having a siloxane structure, bis (3-aminopropyl) tetramethyldisiloxane, bis (paraaminophenyl) octamethylpentasiloxane, and the like can be given.

式（２−Ａ）中、Ａ¹およびＡ²は、酸素原子を表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴の少なくとも一方は、重合性基を含む基であり、重合性基であることが好ましい。The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-A). That is, it is preferable that at least one kind of the polyimide precursor is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further increased.
Formula (2-A)

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

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

  In the polyimide precursor, one type of the repeating unit represented by the formula (2) may be used, or two or more types may be used. Further, the polyimide precursor may include a structural isomer of a repeating unit represented by the formula (2). In addition, the polyimide precursor may include other types of repeating units in addition to the repeating units represented by the above formula (2).

  As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, more preferably 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (2) Is exemplified.

The polyimide precursor is preferably obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. More preferably, the compound is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the dicarboxylic acid or the dicarboxylic acid derivative with a diamine. The polyimide precursor is prepared, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal capping agent which is a monoamine) at a low temperature, a method of reacting a tetracarboxylic dianhydride at a low temperature (partly). Is substituted with a terminal blocking agent that is an acid anhydride or a monoacid chloride compound or a monoactive ester compound) and a diamine compound, a diester is obtained with a tetracarboxylic dianhydride and an alcohol, and then a diamine (partly Is substituted with a terminal capping agent which is a monoamine) in the presence of a condensing agent. Is substituted with a terminal capping agent which is a monoamine).
In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

  In the production of the polyimide precursor, in order to further improve the storage stability, it is preferable to seal with a terminal blocking agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound. Of these, monoamines are more preferably used, and preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6 Aminonaphthalene, 2-carbo C-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, -Aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

In the production of the polyimide precursor, a step of depositing a solid may be included. Specifically, the polyimide precursor in the reaction solution can be precipitated in water and dissolved in a solvent in which the polyimide precursor is soluble, such as tetrahydrofuran, to deposit solid.
Thereafter, the polyimide precursor is dried to obtain a powdery polyimide precursor.

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 further preferably 22,000 to 25,000. Further, the number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and further preferably from 9,200 to 11,200.
The dispersity 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, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less. 3.1 or less is still more preferred, 3.0 or less is still more preferred, and 2.95 or less is especially preferred.

式（４）中、Ｒ¹³¹は、２価の有機基を表し、Ｒ¹³²は、４価の有機基を表す。
重合性基を有する場合、Ｒ¹³¹およびＲ¹³²の少なくとも一方に重合性基を有していてもよいし、下記式（４−１）または式（４−２）に示すようにポリイミドの末端に重合性基を有していてもよい。(Polyimide)
The polyimide is not particularly limited as long as it is a polymer compound having an imide ring. The polyimide is preferably a compound represented by the following formula (4), more preferably a compound represented by the formula (4) and having a polymerizable group.
Equation (4)

In the 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. It may have a polymerizable group.

式（４−１）中、Ｒ¹³³は重合性基であり、他の基は式（４）と同義である。Formula (4-1)

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

式（４−２）中、Ｒ¹³⁴およびＲ¹³⁵の少なくとも一方は重合性基であり、他方は有機基であり、他の基は式（４）と同義である。Formula (4-2)

In 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 are as defined in formula (4).

The polymerizable group that the polyimide preferably has is the same as the polymerizable group that may be contained in R ¹¹³ and R ¹¹⁴ in the formula (2) in the above-mentioned polyimide precursor.

R ¹³¹ in the formula (4) represents a divalent organic group. Examples of the divalent organic group include the same divalent organic groups as those of R ¹¹¹ in Formula (2), and the preferable range is also the same.
R ¹³¹ includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. Specific examples include those exemplified by R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ in the formula (4) is preferably a diamine residue having at least two or more alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing one or both of ethylene glycol chains and propylene glycol chains in one molecule, and further preferably a diamine residue containing no aromatic ring.

Ethylene glycol chain, as the two or more containing diamines together either or both of propylene glycol chain in the molecule, but such examples similar to the diamine can induce R ¹¹¹ and the like in the formula (2), It is not limited to these.

R ¹³² in the formula (4) represents a tetravalent organic group. As the tetravalent organic group represented by R ¹³² , those similar to R ¹¹⁵ in formula (2) are exemplified, and the preferable range is also the same.
For example, four bonds of a tetravalent organic group having the following structure exemplified as R ¹¹⁵ in the formula (2) are bonded to four —C (＝ O) — portions in the above formula (4). Forms a fused ring.

Examples of R ¹³² in the formula (4) include a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. A specific example is the example of R ¹¹⁵ in the formula (2) of the polyimide precursor. 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 preferred that at least one of R ¹³¹ and R ¹³² in the formula (4) has a hydroxy group. More specifically, as R ¹³¹ in the formula (4), 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, (DA-1) to (DA-18) ) Is a preferred example. Preferred examples of R ¹³² in the formula (4) include the above (DAA-1) to (DAA-5).

  Further, the polyimide preferably has a fluorine atom in the structural unit. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

  In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the polyimide. Specifically, as a diamine component for introducing an aliphatic group having a siloxane structure, bis (3-aminopropyl) tetramethyldisiloxane, bis (paraaminophenyl) octamethylpentasiloxane, and the like can be given.

  In addition, in order to improve the storage stability of the photosensitive resin composition, the main chain terminal of the polyimide is sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound. Is preferred. Among these, it is more preferable to use a monoamine. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, and 1-hydroxy-6-aminonaphthalene. , 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-amino Benzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4 , 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

  The polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more. When the imidation ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and the occurrence of substrate warpage can be suppressed.

Polyimide is represented by the above formula (4) containing two or more different types of R ¹³¹ or R ¹³² in addition to the repeating unit represented by the above formula (4) in which all are one kind of R ¹³¹ or R ^132. May be included. Further, the polyimide may include other types of repeating units in addition to the repeating units represented by the above formula (4).

Polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by heating, or may be synthesized directly.
Polyimide obtains a polyimide precursor, a method of completely imidizing it using a known imidation reaction method, or a method of stopping the imidation reaction on the way and partially introducing an imide structure, and further, By blending a completely imidized polymer and its polyimide precursor, it can be synthesized using a method of partially introducing an imide structure.

  Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN).

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

式（３）中、Ｒ¹²¹は、２価の有機基を表し、Ｒ¹²²は、４価の有機基を表し、Ｒ¹²³およびＲ¹²⁴は、それぞれ独立に、水素原子または１価の有機基を表す。(Polybenzoxazole precursor)
The type and the like of the polybenzoxazole precursor are not particularly limited, and preferably include a repeating unit represented by the following formula (3).
Equation (3)

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

R ¹²³ and R ¹²⁴ in Formula (3) each have the same meaning as R ¹¹³ in Formula (2), and the preferred range is also the same. That is, at least one of R ¹²³ and R ¹²⁴ in the formula (3) is preferably a polymerizable group.

R ¹²¹ in the formula (3) represents a divalent organic group. The divalent organic group represented by R ¹²¹ is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. 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 the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two COOHs is used. Are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably from 2 to 30, more preferably from 2 to 25, still more preferably from 3 to 20, and from 4 to It is particularly preferably 15 and more preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluoroseba Acid, 1,9-nonandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid, heptadecandioic acid, octadecandioic acid, nonadecandioic acid, eicosandioic acid, heneicosandioic acid , Docosantioic acid, trichosantioic acid, tetracosantioic acid, pentacosantioic acid, hexacosantioic acid, heptacosantioic acid, octakosantioic acid, nonacosantioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, Glycolic acid, and a dicarboxylic acid represented by the following formula, and the like can be given.

（式中、Ｚは炭素数１〜６の炭化水素基であり、ｎは１〜６の整数である。）

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

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

上記の芳香族基中、Ａは−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂−、および、−Ｃ（ＣＨ₃）₂−からなる群から選択される２価の基を表す。

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

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

R ¹²² in the formula (3) represents a tetravalent organic group. As the tetravalent organic group represented by ^R122 , those similar to ^R115 in the above formula (2) are exemplified, and the preferable range is also the same.
R ¹²² in the formula (3) is preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include, for example, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4 , 4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 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′-diamido -3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4 ' -Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or as a mixture.

  Among the bisaminophenol derivatives, a bisaminophenol derivative having the following aromatic group is preferable.

上記式中、Ｘ₁は−Ｏ−、−Ｓ−、−Ｃ（ＣＦ₃）₂−、−ＣＨ₂−、−ＳＯ₂−、−ＮＨＣＯ−を表す。

In the above formulas, X ₁ is -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - representing the NHCO-.

Formula (As)

In the formula (As), R ₁ represents a hydrogen atom, an alkylene, a substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, a single bond, or a compound represented by the following formula (A- sc) is an organic group selected from 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 a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, which may be the same or different.

（式（Ａ−ｓｃ）中、＊は上記式（Ａ−ｓ）で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。）Formula (A-sc)

(In the formula (A-sc), * indicates that the compound is bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the formula (A-s).)

In the above formula (A-s), it is considered that the substituent at the ortho-position of the phenolic hydroxy group, that is, R ₃ , further shortens the distance between the carbonyl carbon of the amide bond and the hydroxy group. It is particularly preferred in that the effect of achieving a high cyclization rate upon curing is further enhanced.

Further, in the above formula (A-s), when R ₂ is an alkyl group and R ₃ is an alkyl group, it has high transparency to i-line and a high cyclization ratio when cured at a low temperature. The effect can be maintained, which is preferable.

Further, in the above formula (As), it is more preferable that R ₁ is alkylene or substituted alkylene. 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) −, − _{(CH 3) (CH 2 CH} 2 CH 2 CH 2 CH 2 CH 3) - and others as mentioned, -CH ₂ Among them _{-, - CH (CH 3)} -, - C (CH 3) 2 - it is, It is possible to obtain a polybenzoxazole precursor having sufficient balance with sufficient solubility in a solvent while maintaining the effects of high transparency to i-line and high cyclization rate when cured at a low temperature. In this respect, it is more preferable.

  As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 of JP-A-2013-256506 and Example 1 (paragraphs 0189 to 0190). Yes, and their contents are incorporated herein.

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

The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units represented by the above formula (3).
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of substrate warpage due to ring closure of the polybenzoxazole precursor can be suppressed. .

式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ^1sは水素原子または炭素数１〜１０の炭化水素基であり、Ｒ^2sは炭素数１〜１０の炭化水素基であり、Ｒ^3s、Ｒ^4s、Ｒ^5s、Ｒ^6sのうち少なくとも１つは芳香族基で、残りは水素原子または炭素数１〜３０の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分のモル％は、ａ構造は５〜９５モル％、ｂ構造は９５〜５モル％であり、ａ構造およびｂ構造の和は１００モル％である。

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

In the formula (SL), preferred Z includes those wherein R ^5s and R ^6s in the b structure are phenyl groups.
Further, the molecular weight of the diamine residue represented by the formula (SL) is preferably from 400 to 4,000, and more preferably from 500 to 3,000. By setting the molecular weight of the diamine residue represented by the formula (SL) in the above range, the elasticity of the polybenzoxazole precursor after the dehydration and ring closure can be more effectively reduced, and the effect of suppressing the warpage of the substrate and the solvent can be obtained. The effect of improving the solubility can be achieved at the same time.

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29000, and still more preferably 22000 to 28000, when used in the composition described below. Further, the number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and further preferably from 9,200 to 11,200.
The degree of dispersion of the polybenzoxazole precursor is preferably at least 1.4, more preferably at least 1.5, and even more preferably at least 1.6. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, and even more preferably 2.3 or less. It is more preferably 2.2 or less.

式（Ｘ）中、Ｒ¹³³は、２価の有機基を表し、Ｒ¹³⁴は、４価の有機基を表す。
重合性基を有する場合、Ｒ¹³³およびＲ¹³⁴の少なくとも一方に重合性基を有していてもよいし、下記式（Ｘ−１）または式（Ｘ−２）に示すようにポリベンゾオキサゾールの末端に重合性基を有していてもよい。(Polybenzoxazole)
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring. The polybenzoxazole is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X), having a polymerizable group.

In the 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, or as shown in the following formula (X-1) or (X-2), It may have a polymerizable group at the terminal.

式（Ｘ−１）中、Ｒ¹³⁵およびＲ¹³⁶の少なくとも一方は重合性基であり、他方は有機基であり、他の基は式（Ｘ）と同義である。Formula (X-1)

In 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 groups have the same meaning as in formula (X).

式（Ｘ−２）中、Ｒ¹³⁷は重合性基であり、他は置換基であり、他の基は式（Ｘ）と同義である。Formula (X-2)

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

  The polymerizable group that the polybenzoxazole preferably has is the same as the polymerizable group described for the polymerizable group of the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. A specific example is the example of R ¹²¹ in the formula (3) of the polybenzoxazole precursor. Preferred examples are the same as ^R121 .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include the examples of ^R122 in the formula (3) of the polybenzoxazole precursor. Preferred examples are the same as ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² are bonded to a nitrogen atom and an 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.

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

Polybenzoxazole is a compound of the above formula (X) containing two or more different types of R ¹³³ or R ¹³⁴ in addition to the repeating unit represented by the above formula (X), all of which are one type of R ¹³³ or R ^134. May be included. Further, the polybenzoxazole may include other types of repeating units in addition to the repeating units represented by the above formula (X).

Polybenzoxazole may, for example, a bis-aminophenol derivative, a dicarboxylic acid and is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives of the dicarboxylic acids polybenzoxazole precursor including R ^133, which By using a known oxazolation reaction method.
In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like.

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

(Other photosensitive resins)
Even photosensitive resins other than those described above can be applied to the present invention. As other photosensitive resins, epoxy resins, phenol resins, and benzocyclobutene resins can be used.

<<< Polymerizable compound >>>
It is preferable that the resin has a polymerizable group or that the photosensitive resin composition contains a polymerizable compound. With such a configuration, a cured film having more excellent heat resistance can be formed.
The polymerizable compound is a compound having a polymerizable group, and a known compound capable of performing a cross-linking reaction by a radical, an acid, a base, or the like can be used. Examples of the polymerizable group include the polymerizable groups described above for the polyimide precursor. The polymerizable compound may include only one type, or may include two or more types.
The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer or a mixture thereof, and a multimer thereof.

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

The number of functional groups of the polymerizable compound means the number of polymerizable groups in one molecule.
From the viewpoint of developability, the photosensitive resin composition preferably contains at least one kind of bifunctional or more polymerizable compound containing two or more polymerizable groups, and preferably contains at least one kind of trifunctional or more polymerizable compound. Is more preferred.
The photosensitive resin composition preferably contains at least one polymerizable compound having three or more functional groups from the viewpoint that a heat-resistant property can be improved by forming a three-dimensional crosslinked structure. Further, it may be a mixture of a bifunctional or lower functional polymerizable compound and a trifunctional or higher functional polymerizable compound.

  As the polymerizable compound, a compound having a group having an ethylenically unsaturated bond; a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound are preferable.

(Compound containing a group having an ethylenically unsaturated bond)
As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.

  Specific examples of the compound containing a group having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides And multimers thereof. Preferred are esters of an unsaturated carboxylic acid and a polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and a polyamine compound, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy compound, A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and further, a halogen group Also preferred are substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as thiol or a tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. Further, as another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the above unsaturated carboxylic acid.

  Specific examples of the monomer of the ester of the polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, diacrylate Antaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate Oligomers and the like.

  Examples of the methacrylate include 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, bis [para (3-methacryloxy-2 -Hydroxypro ) Phenyl] dimethyl methane, bis - is [para (methacryloxyethoxy) phenyl] dimethyl methane.

  Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

  The crotonic acid ester includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like.

  Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. JP-A-59-5241, JP-A-2-226149, and those having an aromatic skeleton described in JP-A-1-165613, and those containing an amino group described in JP-A-1-165613 are also preferably used. Can be

  Specific examples of the amide monomer of the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis-methacryl. Examples include amide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

  Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition-polymerizable monomers produced by using an addition reaction between an isocyanate and a hydroxy group are also suitable. Specific examples of such a monomer include, for example, a one-molecule molecule described in A urethane compound containing two or more polymerizable vinyl groups in one molecule, in which a polyisocyanate compound having two or more isocyanate groups is added with a vinyl monomer containing a hydroxy group represented by the following formula: .
CH ₂ ＣC (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH
(However, R ⁴ and R ⁵ represent H or CH _3. )
Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-1979. Urethane compounds having an ethylene oxide skeleton described in JP-A-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.

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

As the compound containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100 ° C. or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanate Ethylene oxide or propylene oxide added to polyfunctional alcohols such as nurate, glycerin or trimethylolethane and then (meth) acrylated, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates described in JP-A-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490; Examples include polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having an ethylenically unsaturated group with a cyclic ether group such as glycidyl (meth) acrylate on a polyfunctional carboxylic acid can also be mentioned.
Further, as other compounds containing a group having an ethylenically unsaturated bond, JP 2010-160418 A, JP 2010-129825 A, described in Patent No. 4364216, having a fluorene ring, Compounds having two or more groups having an ethylenically unsaturated bond or cardo resins can also be used.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and JP-A-2-25493. And the like. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. Further, the Journal of the Adhesion Society of Japan, vol. 20, no. 7, pages 300 to 308 (1984) as photopolymerizable monomers and oligomers can also be used.

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

In each of the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. A plurality of R and T in the molecule may be the same or different.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (＝ O) CH ＝ CH ₂ , or —OC (＝ O) represents a group represented by C (CH ₃ ) ＝ CH ₂ .
Specific examples of the compound having a group having an ethylenically unsaturated bond, represented by the above formulas (MO-1) to (MO-5), are described in paragraphs 0248 to 0251 of JP-A-2007-269779. The compounds described above can also be suitably used in the present invention.

  Further, compounds described in formulas (1) and (2) in JP-A-10-62986 together with specific examples thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, are also obtained by polymerization. Can be used as an acidic compound.

  Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187221 can be employed, and the contents thereof are incorporated in the present specification. Particularly, compounds described in paragraphs 0128 to 0130 of the publication are exemplified as preferred embodiments.

Examples of the compound containing a group having an ethylenically unsaturated bond include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (KAYARAD D as a commercial product). -320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues. These oligomer types can also be used.
Further, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2) are also preferable examples.

  Commercially available polymerizable compounds include, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer and SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains manufactured by Sartomer. DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd. (Manufactured by Sanyo Kokusaku Pulp), 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 (Nippon Kayaku Co., Ltd. )), UA-306H, UA-306T, UA-306I, AH-600, T-6 0, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (NOF Co., Ltd.), and the like.

  Compounds containing a group having an ethylenically unsaturated bond are described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Are also suitable. Further, as a polymerizable compound, an addition polymerizable compound having an amino structure or a sulfide structure in a molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238. Monomers can also be used.

The compound containing a group having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound to form an acid group. Is more preferable. Particularly preferably, in a polyfunctional monomer obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is preferably pentaerythritol and / or dicarboxylic acid. Pentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one type may be used alone, or two or more types may be used in combination. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.
The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, it is excellent in production and handleability, and further excellent in developability. Further, the polymerizability is good.

The content of the compound containing a group having an ethylenically unsaturated bond is preferably from 1 to 50% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of good polymerizability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. One compound containing a group having an ethylenically unsaturated bond may be used alone, or two or more compounds may be used in combination.
Further, the mass ratio (resin / polymerizable compound) of the resin and the compound containing a group having an ethylenically unsaturated bond is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90%. / 10 to 50/50 are most preferred. When the mass ratio of the resin to the compound containing a group having an ethylenically unsaturated bond is in the above range, a cured film having excellent polymerizability and heat resistance can be formed.

(Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.

（式中、ｔは、１〜２０の整数を示し、Ｒ⁴は炭素数１〜２００のｔ価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）(AM1)

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

（式中Ｒ⁶は、水酸基または炭素数１〜１０の有機基を示す。）Equation (AM2) Equation (AM3)

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

  The compound represented by the formula (AM1) is preferably from 5 parts by mass to 40 parts by mass 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. Further, in all the polymerizable compounds, a compound represented by the following formula (AM4) is contained in an amount of 10% by mass or more and 90% by mass or less, and a compound represented by the following formula (AM5) is contained in the total thermal crosslinking agent by 10% by mass or more. It is also preferable to contain 90 mass% or less.

（式中、Ｒ⁴は炭素数１〜２００の２価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）(AM4)

(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 (AM3).)

（式中ｕは３〜８の整数を示し、Ｒ⁴は炭素数１〜２００のｕ価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）Equation (AM5)

(Wherein 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 (AM3)) .)

（式中Ｒ⁶は、水酸基または炭素数１〜１０の有機基を示す。）Equation (AM2) Equation (AM3)

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

  Within this range, cracks are less likely to occur when the composition is formed on an uneven substrate. It is excellent in pattern workability and can have high heat resistance such that the 5% mass reduction temperature is 350 ° C. or more, more preferably 380 ° C. or more. Specific examples of the compound represented by the formula (AM4) include 46DMOC and 46DMOP (trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-dimethoxymethyl-p-cresol, etc. Is mentioned .

  Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Material Industry Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 and NIKALAC MW-100LM (trade 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 photo-radical 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 irradiated with light. In addition, curing due to radicals occurs, and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern in which only the electrode portion is masked, there is an advantage that regions having different solubility can be easily formed according to the pattern of the electrode. is there.

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

  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, and those having a trihalomethyl group), Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and azo compounds Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like.

  Examples of halogenated hydrocarbon compounds having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compound described in British Patent No. 1388492, the compound described in JP-A-53-133428, the compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. Compounds described in 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, U.S. Pat. And the compounds described in Japanese Patent No. 4212976.

  As the compounds described in U.S. Pat. No. 4,221,976, for example, compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-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)- , 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.).

  In addition, as a photopolymerization initiator other than the above, compounds described in paragraph 0086 of JP-A-2005-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, And the compounds described in U.S. Pat. No. 3,615,455, and the like, the contents of which are incorporated herein.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
Among commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225988 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

An oxime compound is more preferably used as the photopolymerization initiator. By using the oxime compound, the exposure latitude can be more effectively improved. Oxime ester compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
As specific examples of the oxime compound, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, the following compounds, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimiminobtan-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 -Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of the oxime compound include: C. S. Perkin II (1979) pp. 1653-1660; C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in each of documents 202-232, compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-T-2004-534797, JP-A-2006-342166, International Publication WO2015 And the compounds described in each publication of JP / A 036910.
As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF) and Adeka Optomer N-1919 (available from ADEKA Corporation, JP 2012-14052A) A polymerization initiator 2) is also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Aquel's NCI-831 and Adeka Aquel's NCI-930 (manufactured by ADEKA) can be used. DFI-091 (manufactured by Daito Mix) can also be used.

最も好ましいオキシム化合物は、特開２００７−２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９−１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。Further, a compound described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position, a compound described in U.S. Pat. JP-A-2010-15025 and compounds disclosed in U.S. Patent Publication 2009-292039, ketoxime compounds described in International Publication WO2009-131189, and U.S. Pat. Compounds such as those described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source, may be used.
Further, cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compound condensed to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 has high light absorption and high sensitivity. preferable.
Further, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 Compound (C-3) described in paragraph 0101 of JP-A-164471. Specific examples include the following compounds.

The most preferred oxime compounds include oxime compounds having a specific substituent described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061.

式（Ｉ）中、Ｒ⁵⁰は、炭素数１〜２０のアルキル基；１個以上の酸素原子によって中断された炭素数２〜２０のアルキル基；炭素数１〜１２のアルコキシ基；フェニル基；炭素数１〜２０のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数１〜１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２〜１８のアルキル基および炭素数１〜４のアルキル基の少なくとも１つで置換されたフェニル基；またはビフェニリルであり、Ｒ⁵¹は、式（ＩＩ）で表される基であるか、Ｒ⁵⁰と同じ基であり、Ｒ⁵²〜Ｒ⁵⁴は各々独立に炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシまたはハロゲンである。

式中、Ｒ⁵⁵〜Ｒ⁵⁷は、上記式（Ｉ）のＲ⁵²〜Ｒ⁵⁴と同じである。From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. Are preferred.
Further preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is particularly preferred.
The photopolymerization initiator may be N, N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl- Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, and alkylanthraquinone; Also, quinones condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can be used.
Further, a compound represented by the following formula (I) can also be used.

In the formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by at least one oxygen atom; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C1-C12 alkenyl group, C2-C2 interrupted by one or more oxygen atoms A phenyl group substituted with at least one of an alkyl group having 18 and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, wherein R ⁵¹ is a group represented by the formula (II) or the same as R ⁵⁰ R ^{52 to} R ⁵⁴ are each independently alkyl having 1 to 12 carbons, alkoxy or halogen having 1 to 12 carbons.

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

  Further, 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 is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 30% by mass, based on the total solid content of the photosensitive resin composition. To 20% by mass, more preferably 0.1 to 10% by mass.
The photopolymerization initiator may be only one type or two or more types. When two or more photopolymerization initiators are used, the total is preferably within the above 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 movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition.
The migration inhibitor is not particularly limited, but may be a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, A compound having a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), a compound having thioureas and a mercapto group, a hinder phenol compound, Salicylic acid derivative compounds and hydrazide derivative compounds are exemplified. Particularly, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

  Further, an ion trapping agent for trapping anions such as halogen ions can also be used.

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

  Specific examples of the migration inhibitor 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 is preferably 0.01 to 5.0% by mass, and more preferably 0.05 to 5.0% by mass based on the total solid content of the photosensitive resin composition. 2.0 mass% is more preferable, and 0.1 to 1.0 mass% is still more preferable.
The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably within the above range.

<<< Polymerization inhibitor >>>
The photosensitive resin composition used in the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, and 4,4′-thiobis (3-methyl -6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, Ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis ( 4-Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds 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 based on the total solid content of the photosensitive resin composition.
Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably within the above 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, but is selected from an acidic compound which generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an anion of 0 to 4 and an ammonium cation having a pKa of 0 to 4. It is preferable to include at least one kind of thermal base generator. Here, pKa1, represents the logarithm (-Log ₁₀ Ka) of the dissociation constant of the first proton acid (Ka), the details will be described later.
By compounding such a compound, a cyclization reaction of the polyimide precursor and the polybenzoxazole precursor can be performed at a low temperature, and a composition having more excellent stability can be obtained. In addition, since the thermal base generator does not generate a base unless heated, even if it coexists with the polyimide precursor and the polybenzoxazole precursor, the cyclization of the polyimide precursor and the polybenzoxazole precursor during storage, etc. And has excellent storage stability.

The thermal base generator contains at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having an pKa of 0 to 4 and an ammonium cation. Is preferred.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote a cyclization reaction of a polyimide precursor, a polybenzoxazole precursor, and the like, The cyclization of the polyimide precursor and the polybenzoxazole precursor can be performed at a low temperature. In addition, even if these compounds coexist with a polyimide precursor and a polybenzoxazole precursor that are cyclized and cured by a base, the cyclization of the polyimide precursor and the polybenzoxazole precursor almost progresses unless heated. Therefore, a photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, and the like having excellent stability can be prepared.
In the present specification, an acidic compound refers to a compound obtained by collecting 1 g of a compound in a container, adding 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio: water / tetrahydrofuran = 1/4), and adding the compound for 1 hour at room temperature. A solution obtained by stirring and using a pH (power of hydrogen) meter at 20 ° C. means a compound whose value is less than 7.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C. or higher, more preferably 135 ° C. or higher.
When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is hardly generated during storage, and therefore, a polyimide precursor and a polybenzoxazole precursor with excellent stability are included. A photosensitive resin composition can be prepared. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. The base generation temperature is measured by, for example, differential scanning calorimetry, heating the compound in a pressure-resistant capsule at 250C at 5C / min, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Tertiary amines have a high basicity, and can lower the cyclization temperature of polyimide precursors and polybenzoxazole precursors. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher.
The molecular weight of the generated base is preferably from 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

  In the present invention, the acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by the following formula (101) or (102).

  In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.) or 40 ° C. or higher (preferably 120 to 200 ° C.). The compound may be a compound excluding an acidic compound which generates a base when heated to the step (1).

式（１０１）および式（１０２）中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ⁷は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ¹とＲ²、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁵とＲ⁷はそれぞれ結合して環を形成してもよい。In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or (102) and an anion. The anion may be bonded to any part of the ammonium cation through a covalent bond, may be present outside the ammonium cation molecule, or may be present outside the ammonium cation molecule. preferable. In addition, that an anion has outside the molecule of an ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, an anion outside the molecule of the cation portion is also referred to as a counter anion.
Equation (101) Equation (102)

In the formulas (101) and (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 the formulas (101) and (102) may be bonded to each other to form a ring.

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

In Formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ have the same meaning as in Formula (101) or Formula (102).
In the 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 to 5. .

In the present invention, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is preferably 3.5 or less, more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor and the polybenzoxazole precursor can be cyclized at a low temperature, and the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor can be further improved. Can be improved. When the pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, and the like can be suppressed. The properties are good. When pKa1 is 0 or more, the generated base is difficult to be neutralized, and the cyclization efficiency of the polyimide precursor and the polybenzoxazole precursor is good.
The type of the anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and is more preferably a carboxylate anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability, and developability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, and the like. In particular, by using a divalent carboxylic acid anion, the stability, curability, and developability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, and the like can be further improved.
In the present invention, the carboxylate anion is preferably a carboxylate anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, even more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, which is determined by Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, Hafliger). Compiled by: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R., R.M. al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software will be used.

式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。The carboxylate anion is preferably represented by the following formula (X1).

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

In the present invention, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described by Yuho Tsuno, Journal of the Society of Synthetic Organic Chemistry, Vol. 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 documents.
Examples of the substituent in which σm has a positive value include, for example, a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), a HC≡C group (σm = 0.21), CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06) and the like. 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は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシ基またはカルボキシル基を表し、Ａｒは芳香族基を表す。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In 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 hydroxy group or a carboxyl group, and Ar represents an aromatic group. Represents

式（ＸＡ）において、Ｌ¹⁰は、単結合、または、アルキレン基、アルケニレン基、芳香族基、−ＮＲ^X−およびこれらの組み合わせから選ばれる２価の連結基を表し、Ｒ^Xは、水素原子、アルキル基、アルケニル基またはアリール基を表す。In the present invention, the carboxylate anion is preferably represented by the following formula (XA).
Formula (XA)

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

  Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

Specific examples of the thermal base generator include the following compounds.

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 based on the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
One or two or more thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

金属接着性改良剤は樹脂１００質量部に対して好ましくは０．１〜３０質量部であり、さらに好ましくは０．５〜１５質量部の範囲である。０．１質量部以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、３０質量部以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。
金属接着性改良剤は１種類のみでもよいし、２種類以上であってもよい。２種類以上用いる場合は、その合計が上記範囲であることが好ましい。<<< Metal adhesion improver >>>
It is preferable that the photosensitive resin composition used in the present invention contains a metal adhesion improver for improving the adhesion to a metal material used for an electrode or a wiring. Examples of the metal adhesion improver include sulfide compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and paragraphs 0032 to 0043 of JP-A-2013-072935. The following compounds (such as N- [3- (triethoxysilyl) propyl] maleic acid monoamide) are also exemplified as metal adhesion improvers.

The amount of the metal adhesion improver is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, based on 100 parts by mass of the resin. When the amount is 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the curing step becomes good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing step are good. Become.
Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<<< Solvent >>>
When the photosensitive resin composition used in the present invention is formed into a layer by coating, it is preferable to add a solvent. Known solvents can be used without limitation as long as the photosensitive resin composition can be formed in a layered form. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, etc.)) ), 3-hydroxypropionate alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate) , 3 Ethyl ethoxypropionate)), alkyl 2-oxypropionates (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate, and 2-oxy-2-methylpropionic acid Ethyl (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Methyl oxobutanoate, 2-oxo Ethyl Tan acid and the like preferably.
As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferably mentioned.
Dimethyl sulfoxide is preferably used as the sulfoxide.

  From the viewpoint of improving the state of the coated surface, a form in which two or more solvents are mixed is also preferable. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone Dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and a mixed solution composed of two or more types selected from propylene glycol methyl ether acetate are preferable. Particularly preferred is a combination of dimethyl sulfoxide and γ-butyrolactone.

When the photosensitive resin composition has a solvent, the content of the solvent is preferably set to an amount such that the total solid content of the photosensitive resin composition becomes 5 to 80% by mass from the viewpoint of applicability. 70 mass% is more preferable, and 10 to 60 mass% is particularly preferable. The content of the solvent may be adjusted according to a desired thickness and a coating method. For example, when the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, more preferably 1.0% by mass to 25% by mass. By adjusting the content of the solvent according to the coating method, a photosensitive resin composition layer having a desired thickness can be formed uniformly.
The solvent may be only one kind or two or more kinds. When two or more solvents are used, the total is preferably within the above range.
Further, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is determined based on the total mass of the photosensitive resin composition from the viewpoint of film strength. Is preferably less than 5% by mass, more preferably less than 1% by mass, particularly preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass.

<<<< Other additives >>>>
The photosensitive resin composition used in the present invention is, as long as the effects of the present invention are not impaired, if necessary, various types of additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, and a silane. Coupling agents, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, etc. can be compounded. . When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photo base generator)
The photosensitive resin composition used in the present invention may contain a photobase generator. Photobase generators are those that generate a base upon exposure to light and do not show activity under normal conditions of normal temperature and normal pressure. However, when irradiated with electromagnetic waves and heated as an external stimulus, the base (basic substance) ) Is not particularly limited as long as it generates). The base generated by the exposure acts as a catalyst when the polyimide precursor and the benzoxazole precursor are cured by heating, and thus can be suitably used in a negative type.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and may be a general content. The photobase generator is preferably in the range of 0.01 part by mass or more and less than 30 parts by mass, more preferably in the range of 0.05 part by mass to 25 parts by mass, based on 100 parts by mass of the resin. More preferably, the amount is in the range of 0.1 to 20 parts by mass.
The photobase generator may be only one type, or two or more types. When two or more photobase generators are used, the total is preferably within the above range.

In the present invention, known photobase generators can be used. For example, M. Shirai, and M.S. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); Kutal, Coord. Chem. Rev .. , 211, 353 (2001); Kaneko, A .; Sarker, and D.S. Neckers, Chem. Mater. H., 11, 170 (1999); Tachi, M .; Shirai, and M.S. Tsunooka, J .; Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J .; Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J .; Photopolym. Sci. Technol. , 19, 81 (2006), a transition metal compound complex, a compound having a structure such as an ammonium salt, or a compound in which an amidine moiety is latentized by forming a salt with a carboxylic acid. Ionized compounds in which the base component is neutralized by forming a salt, and nonionic compounds in which the base component is latentized by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound. Can be mentioned.
Photobase generators that can be used in the present invention are not particularly limited, and known photobase generators can be used.For example, carbamate derivatives, amide derivatives, imide derivatives, α cobalt complexes, imidazole derivatives, cinnamamide derivatives, Oxime derivatives and the like.
Examples of the photobase generator include a photobase generator having a cinnamic acid amide structure as disclosed in JP-A-2009-80452 and International Publication WO2009 / 123122, JP-A-2006-189591, and JP-A-2006-189591. Photobase generator having a carbamate structure as disclosed in JP 2008-247747, oxime structure and light having a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581. Examples include, but are not limited to, base generators, and other known photobase generators can also be used.
Other examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP-A-2012-93746, compounds described in paragraphs 0022 to 0069 of JP-A-2013-194205, and The compounds described in paragraphs 0026 to 0074 of JP2013-204019A, and the compounds described in paragraph 0052 of WO2010 / 064631 are mentioned as examples.

(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.
A thermal radical polymerization initiator is a compound that generates a radical by the energy of heat and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is advanced. In addition, when the polyimide precursor and the polybenzoxazole precursor contain an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor and the polybenzoxazole precursor proceeds with the cyclization of the polyimide precursor and the polybenzoxazole precursor. Therefore, higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the photosensitive resin composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably from 0.1 to 50% by mass relative to the total solid content of the photosensitive resin composition, and from 0.1 to 50% by mass. 30 mass% is more preferable, and 0.1 to 20 mass% is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance.
One kind of thermal radical polymerization initiator may be used, or two or more kinds may be used. When two or more thermal radical polymerization initiators are used, the total is preferably within the above range.

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

  Examples of the thermal acid generator include those described in paragraph 0055 of JP-A-2013-072935.

  Further, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferable as the thermal acid generator.

The content of the thermal acid generator is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor. When the content is 0.01 part 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. In addition, from the viewpoint of electrical insulation of the cured film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less.
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 within the above 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 the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and JP-A-2014-191252. The compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 099754 are exemplified. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358.
The amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin. When the amount is 0.1 part by mass or more, more sufficient adhesion to the substrate can be provided, and when the amount is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
Only one silane coupling agent may be used, or two or more silane coupling agents may be used. When two or more types are used, the total amount is preferably within the above range.

(Sensitizing dye)
The photosensitive resin composition used in the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific actinic radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, or the like, and causes effects such as electron transfer, energy transfer, and heat generation. As a result, the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.

  Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in a range of 300 nm to 450 nm. For example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Eg, 2,4-diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (Eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-di) Chiruamino 4-methylcoumarin), styryl benzenes, distyryl benzenes, and the like carbazoles like.

  When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably from 0.01 to 20% by mass, and more preferably from 0.1 to 15% by mass, based on the total solid content of the photosensitive resin composition. Is more preferable, and 0.5 to 10% by mass is further preferable. The sensitizing dyes may be used alone or in combination of two or more.

(Chain transfer agent)
The photosensitive resin composition used in the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate a radical by donating hydrogen to a low activity radical, or can generate a radical by being oxidized and then deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used.

When the photosensitive resin composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. It is 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.

(Surfactant)
Each type of surfactant may be added to the photosensitive resin composition used in the present invention from the viewpoint of further improving coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

When the photosensitive resin composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0 to 2.0% by mass, based on the total solid content of the photosensitive resin composition. 0.005 to 1.0% by mass.
The surfactant may be only one kind or two or more kinds. When two or more surfactants are used, the total is preferably within the above range.

(Higher fatty acid derivatives)
To the photosensitive resin composition used in the present invention, in order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the composition is dried in the course of application. May be unevenly distributed on the surface.
When the photosensitive resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.
Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<<< Characteristics of photosensitive resin composition >>>
Next, the characteristics of the photosensitive resin composition used in the present invention will be described.
It is preferable that the photosensitive resin composition used in the present invention has a crosslinked structure constructed by exposure to light and has reduced solubility in an organic solvent. By having a crosslinked structure, the adhesion between the layers can be increased when the photosensitive resin composition layers are laminated. Further, the solubility of the photosensitive resin composition layer in the organic solvent is reduced by the exposure, which is advantageous when a deep groove or a deep hole is provided when the number of layers increases.
The water 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 the coated surface condition.

The metal content of the photosensitive resin composition used in the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulation. . Examples of the metal 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 within the above range.
Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition, a material having a low metal content is selected as a material constituting the photosensitive resin composition, The raw material to be filtered may be filtered, or the apparatus may be lined with polytetrafluoroethylene or the like to carry out distillation under the condition that contamination is suppressed as much as possible.

  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, from the viewpoint of wiring corrosion. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine and bromine atoms or the sum of chloride and bromide ions is within the above range.

<Drying process>
The method for producing a cured film of the present invention may include a step of drying the solvent after forming the photosensitive resin composition layer. The preferred drying temperature is from 50 to 150C, more preferably from 70 to 130C, even more preferably from 90 to 110C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, and even more preferably 3 minutes to 7 minutes.

<Exposure process>
The method for producing a cured film of the present invention includes an exposure step of exposing the photosensitive resin composition layer. The conditions for the exposure are not particularly limited, and it is preferable that the solubility of the exposed portion of the photosensitive resin composition in the developing solution can be changed, and it is more preferable that the exposed portion of the photosensitive resin composition can be cured. For example, exposure of the photosensitive resin composition layer, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, it is more preferable to irradiate 200~8000mJ / cm ^2.
The exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, and preferably 240 to 550 nm.

  Exposure may be performed by pattern exposure, or exposure may be performed by uniform irradiation over the entire surface.

<Development process>
The method for producing a cured film of the present invention includes a developing step of performing a developing treatment on the exposed photosensitive resin composition layer.
The development processing step is preferably a negative development processing step. By performing the negative developing process, the unexposed portions (non-exposed portions) are removed. The developing method is not particularly limited, and it is preferable that a desired pattern can be formed. For example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
In the present invention, it is preferable to carry out the developing step even when performing exposure with uniform irradiation over the entire surface.
The development is preferably performed using a developer. The developer can be used without any particular limitation as long as the portion that is not exposed (unexposed portion) is removed. Development with an organic solvent is preferred.As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate) , Ethyl ethoxyacetate, etc.), alkyl 3-oxypropionates (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-D Methyl xypropionate, ethyl 3-ethoxypropionate)), alkyl 2-oxypropionates (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2- Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate , Ethyl acetoacetate, 2-oxo Methyl butanoate, ethyl 2-oxobutanoate, and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.
Examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.
Dimethyl sulfoxide is preferably used as the sulfoxide.
Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, 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 from 10 seconds to 5 minutes.
The temperature at the time of development is not particularly limited, but can be usually 20 to 40 ° C.
After the treatment using the developer, rinsing may be further performed. Rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The rinsing time is preferably from 5 seconds to 1 minute.

<Curing process>
The method for producing a cured film of the present invention includes a curing step of curing the photosensitive resin composition layer after the development processing,
The curing process
A temperature raising step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature,
A cooling step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.

  The curing step (particularly, the temperature raising step and the holding step) is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the resin. The oxygen concentration is preferably at most 50 ppm by volume, more preferably at most 20 ppm by volume.

<< temperature rise process >>
The temperature raising step is a step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature.
In the temperature raising step, it is preferable to advance a cyclization reaction of the resins (preferably, a polyimide precursor and a polybenzoxazole precursor) contained in the photosensitive resin composition layer. For example, a polyimide or polybenzoxazole can form a three-dimensional network structure when heated with a crosslinking agent. In addition, curing of the unreacted radically polymerizable compound can be advanced.
It is preferable that the final temperature in the temperature raising step is the imidization temperature of the resin contained in the photosensitive resin composition layer.
It is preferable that the final temperature in the temperature raising step be the maximum heating temperature. The maximum heating temperature is preferably from 100 to 500C, more preferably from 150 to 450C, even more preferably from 160 to 350C.

The heating step is preferably performed at a heating rate of 1 to 12 ° C / min from a temperature of 20 to 150 ° C to a maximum heating temperature, more preferably 2 to 11 ° C / min, and still more preferably 3 to 10 ° C / min. preferable. By setting the heating rate to 1 ° C./min or more, the amine can be prevented from being excessively volatilized while securing the productivity. By setting the heating rate to 12 ° C./min or less, the cured film can be cured. Residual stress can be reduced.
The temperature at the start of heating is preferably from 20 to 150C, more preferably from 20C to 130C, even more preferably from 25C to 120C. The temperature at the start of heating refers to the heating temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is dried after being applied on a substrate, the temperature is the temperature after the drying, for example, gradually from the boiling point of the solvent contained in the photosensitive resin composition − (30 to 200) ° C. It is preferable to raise the temperature.

  The heating may be performed stepwise. For example, before the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./minute, the temperature is raised at 180 ° C. for 60 minutes, the temperature is raised from 180 ° to 200 ° C. at 2 ° C./minute, and the temperature is set at 200 ° C. for 120 minutes. A processing step may be performed. The heating temperature in the pretreatment step is preferably 100 to 200C, more preferably 110 to 190C, and most preferably 120 to 185C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating UV as described in US Pat. No. 9,159,547. By such a pretreatment step, it is possible to improve the characteristics of the cured film. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment step may be a two or more-step process. For example, the pretreatment step 1 may be performed in a range of 100 to 150 ° C., and the pretreatment step 2 may be performed in a range of 150 to 200 ° C.

  The heating step is preferably performed for 20 to 200 minutes, more preferably for 20 to 100 minutes, and particularly preferably for 20 to 60 minutes.

<< Holding Step >>
The method for producing a cured film according to the present invention preferably includes a holding step of holding at a holding temperature equal to the ultimate temperature of the heating step for 30 minutes or more after the heating step and before the cooling step.
After reaching the final temperature of the temperature raising step, heating is preferably performed at a holding temperature equal to the final temperature of the temperature raising step for 30 to 360 minutes, more preferably for 30 to 300 minutes, and more preferably 30 to 240 minutes. It is particularly preferable to perform heating for a minute, and it is more particularly preferable to perform heating for 60 to 240 minutes.
The holding temperature in the holding step is preferably from 150 to 450 ° C, more preferably from 160 to 350 ° C.

<< cooling process >>
The cooling step is a step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.
The cooling rate in the cooling step is preferably 2 ° C./min or less, more preferably 1 ° C./min or less. The cooling rate in the cooling step is preferably 0.1 ° C./min or more from the viewpoint of the processing time.
It is preferable from the viewpoint of stress relaxation that the cooling rate in the cooling step is lower than the heating rate in the heating step.

The cooling step is preferably performed for 30 to 600 minutes, more preferably 60 to 600 minutes.
In the method for producing a cured film of the present invention, it is preferable that the time of the cooling step is longer than the time of the temperature raising step from the viewpoint of stress relaxation.

In the method for producing a cured film of the present invention, the final temperature of the cooling step is preferably 30 ° C. or lower than the glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing step. . If the final temperature of the cooling step is lowered to a temperature lower by at least 30 ° C. than the Tg of the photosensitive resin composition layer, the polyimide is sufficiently cured and the occurrence of delamination is easily suppressed.
The ultimate temperature of the cooling step is more preferably lower by 10 to 60 ° C, particularly preferably lower by 40 to 60 ° C, than the glass transition temperature of the photosensitive resin composition layer after the curing step.

<< Step of bringing to room temperature >>
After the photosensitive resin composition layer reaches the final temperature of the cooling step, it is preferable to include a step of cooling the photosensitive resin composition layer at an arbitrary temperature lowering rate to reach room temperature.
The temperature decreasing rate in the step of bringing the temperature to room temperature is not particularly limited, and is preferably higher than the temperature decreasing rate in the cooling step. The temperature decreasing rate in the step of bringing the temperature to room temperature can be, for example, 5 to 10 ° C./min.

<Curing film>
<< Tg >>
The glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing step is preferably from 180 to 230 ° C.

<< Residual stress >>
The residual stress of the photosensitive resin composition layer (cured film) after the curing step, measured according to a laser measurement method, is preferably less than 35 MPa, more preferably less than 25 MPa, and particularly preferably less than 15 MPa.

[Production method of laminate]
The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention,
The method further includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step.
With the above configuration, the method for manufacturing a laminate of the present invention can suppress delamination when a substrate, a cured film, and a metal layer are laminated.
Here, in the method for producing a laminate of the present invention, it is preferable that the step of forming the photosensitive resin composition layer, the step of exposing, the step of developing, and the step of curing are repeated in the above order. In the method for producing a laminate of the present invention, the photosensitive resin composition layer forming step, the exposing step, the developing step, the curing step, the heating step, the cooling step, and the metal layer forming step can be performed again in the above order. preferable. When at least one of the cured film and the metal layer is two or more, the heating and cooling steps are repeated, so that the effect of suppressing delamination particularly when the substrate, the cured film, and the metal layer are laminated is large.

<Metal layer forming step>
The method for producing a laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step.
The method for producing a laminate includes a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step, and the photosensitivity after the curing step when forming the metal layer. It is preferable that the temperature of the resin composition layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.

In the method for producing a laminate, the temperature of the photosensitive resin composition layer at the time of 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. It is particularly preferable that the temperature is lower by 100 to 200 ° C.
When two or more metal layers are formed in the metal layer forming step, at least after the curing step in forming a metal layer (preferably a barrier metal film) that directly contacts the photosensitive resin composition layer after the curing step The temperature of the photosensitive resin composition layer is preferably in the above range. When two or more metal layers are formed in the metal layer forming step, the temperature of the photosensitive resin composition layer after the curing step in forming the second metal layer is not particularly limited. However, if there is a portion directly provided on the photosensitive resin composition layer even in the second metal layer, the photosensitive resin composition layer after the curing step when forming the second metal layer Is preferably within the above range.
In particular, when the second metal layer is formed by vapor deposition, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer may be in the above range. preferable. When the second metal layer is formed using non-vapor phase film formation (plating or the like), generally, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is formed. Is below the glass transition temperature of the photosensitive resin composition layer.

  The metal layer formed in the metal layer forming step is not particularly limited, and an existing metal can be used. Examples of the metal include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, and compounds (including alloys) containing at least one of these. More preferably, the metal layer formed in the metal layer forming step contains at least one of titanium, tantalum and copper and a compound containing at least one of them, and titanium and copper and at least one of these compounds. It is particularly preferable that at least one of the compounds is contained, and it is more preferable that copper is contained. The metal included in the metal layer formed in the metal layer forming step may be one type or two or more types.

In the method for manufacturing a laminate of the present invention, the thickness of the metal layer formed in the metal layer forming step is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and more preferably 100 to 300 nm. Is particularly preferred.
In the method for producing a laminate of the present invention, the metal layer formed in the metal layer forming step may be one layer or two or more layers.
When one metal layer is formed in the metal layer forming step, the metal layer is preferably used as a barrier metal film.
When two or more metal layers are formed in the metal layer forming step, the thickness of the entire metal layer formed in the metal layer forming step is preferably in the above range. When there are two or more metal layers formed in the metal layer forming step, the metal layer formed in the metal layer forming step 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 length of penetration of the metal into the cured film. It is preferable that the type of the metal of the barrier metal film is the metal described above as the metal included in the metal layer formed in the metal layer forming step. The thickness of the barrier metal film is preferably from 50 to 2,000 nm, more preferably from 50 to 1,000 nm, and particularly preferably from 100 to 300 nm.
The seed layer is preferably a layer for facilitating the formation of the pattern of the second metal layer formed in the second metal layer forming step. The kind of the metal of the seed layer is preferably the same kind of metal as the second metal layer formed in the second metal layer forming step. The thickness of the seed layer is preferably from 50 to 2,000 nm, more preferably from 50 to 1,000 nm, and particularly preferably from 100 to 300 nm.

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

<Second metal layer forming step>
It is preferable that the method for producing a laminate of the present invention further includes a second metal layer forming step of forming a second metal layer on the surface of the metal layer.

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

  In the method for manufacturing a laminate, the thickness of the second metal layer formed in the second metal layer forming step is, for example, 3 to 50 μm, preferably 3 to 10 μm, and more preferably 5 to 10 μm. Is more preferable, and particularly preferably 5 to 7 μm. When manufacturing a laminate for power semiconductor use, the thickness of the second metal layer formed in the second metal layer forming step is preferably 35 to 50 μm.

The method for forming the second metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, chemical vapor deposition (CVD), electrolytic plating, electroless plating, etching, printing, and a method combining these are conceivable. More specifically, there are a patterning method combining photolithography and etching, a patterning method combining photolithography and electrolytic plating, and a patterning method combining photolithography, electrolytic plating and etching.
As a patterning method combining photolithography and electrolytic plating, after forming a seed layer of a metal layer formed in a metal layer forming step by sputtering, a pattern of a seed layer is formed by photolithography, and the patterned seed is formed. A method in which electrolytic plating is performed on the layer to form a second metal layer is preferable. Thereafter, etching may be further performed to remove a seed layer in a region where the second metal layer is not formed.

<Surface activation treatment step>
The method for producing a laminate may include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment.
Generally, the surface activation treatment step is preferably performed after the metal layer forming step. After the curing step, the metal layer may be formed after performing a surface activation treatment step on the photosensitive resin composition layer.
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the photosensitive resin composition layer after the curing step, or may be performed on the metal layer and the photosensitive layer after the curing step. The process may be performed on at least a part of both of the conductive resin composition layers. The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is preferably performed on part or all of a region of the metal layer on which a photosensitive resin composition layer is further formed. Is more preferred. As described above, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the cured film provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is also performed on part or all of the photosensitive resin composition layer (cured film) after the curing step. As described above, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion to the metal layer or the cured film provided on the surface subjected to the surface activation treatment. When performing negative tone development, the exposed portion is subjected to a surface treatment, and the strength of the film is improved by curing or the like, so that the photosensitive resin composition layer (cured film) is not damaged.
As the surface activation treatment, specifically, plasma treatment of each kind of source gas (oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, and argon and oxygen mixed gas, etc.); corona discharge treatment; CF Etching using mixed gas of ₄ and O _2, mixed gas of NF ₃ and O ₂ , SF ₆ , NF ₃ , and mixed gas of NF ₃ and O ₂ ; Surface treatment using ultraviolet (UV) ozone method; Immersion in an organic surface treatment agent containing a compound having at least one type of amino group and thiol group after removing the oxide film by immersion in a substrate; preferably, selected from mechanical roughening treatment using a brush . Plasma treatment is more preferable, and oxygen plasma treatment using oxygen as a source gas is particularly preferable. For corona discharge treatment, the energy is preferably 500~200000J / m ^2, more preferably 1000~100000J / m ^2, more preferably 10000~50000J / m ^2.

<Lamination process>
The method for producing a laminate of the present invention preferably further includes a laminating step after the metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step.
The laminating step is a series of steps including performing the photosensitive resin composition layer forming step, the exposing step, the developing step, and the curing step again in the above order.
The laminating step is preferably a step in which the photosensitive resin composition layer forming step, the exposing step, the developing step, and the curing step are performed again in the above order.

When the laminating step is further performed after the laminating step, the surface activation processing step can be further performed after the exposing step or after the metal layer forming step.
The lamination step is preferably performed 3 to 7 times, more preferably 3 to 5 times.
For example, a configuration of three to seven cured films is preferable, such as a cured film / metal layer / cured film / metal layer / cured film / metal layer, and more preferably three to five layers. As the number of layers increases, the photosensitive resin composition layer is repeatedly exposed to a developing solution, a metal etching treatment, and a high temperature treatment in a curing step. Therefore, the metal layer / cured film interface or the cured film interface resulting from the method for producing a laminate of the present invention, or This has the effect of suppressing the occurrence of delamination at the interface between the cured film and the cured film.
With such a configuration, the photosensitive resin composition layer (cured film) and the metal layer can be alternately laminated, and can be used as a multilayer wiring structure of a semiconductor element such as a redistribution layer.
It is preferable that the thickness of the photosensitive resin composition layer (cured film) increases as the lamination goes upward.

[Semiconductor element manufacturing method]
The method for manufacturing a semiconductor device of the present invention includes the method for manufacturing a laminate of the present invention.
With the above configuration, the method for manufacturing a semiconductor device of the present invention can provide a semiconductor device in which delamination is suppressed when a substrate, a cured film, and a metal layer are stacked.

Hereinafter, one embodiment of a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention will be described.
FIG. 1 is a schematic diagram showing a configuration of an embodiment of a semiconductor device. A semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor chip 101 in which a plurality of semiconductor chips 101a to 101d are stacked is arranged on a wiring board 120.
In this embodiment, the case where the number of stacked semiconductor chips is four is mainly described, but the number of stacked semiconductor chips is not particularly limited. For example, two, eight, sixteen, There may be 32 layers or the like. Further, it may be a single layer.

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

The semiconductor chip 101 has a structure in which a semiconductor chip 101a having no through electrode and a semiconductor chip 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pads of the semiconductor chip 101a having no through electrodes and the connection pads on the semiconductor chip 101a side of the semiconductor chip 101b having the through electrodes 102b adjacent thereto are connected by metal bumps 103a such as solder bumps. . A connection pad on the other side of the semiconductor chip 101b having the through electrode 102b is connected to a connection pad on the semiconductor chip 101b side of the semiconductor chip 101c having the through electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. . Similarly, the connection pad on the other side of the semiconductor chip 101c having the through electrode 102c is connected to the connection pad on the semiconductor chip 101c side of the semiconductor chip 101d having the through electrode 102d adjacent thereto by a metal bump 103c such as a solder bump. Have been.

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

The semiconductor chip 101 is stacked on the wiring board 120.
As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

On one surface of the wiring board 120, a surface electrode 120a is provided.
An insulating layer 115 on which a rewiring layer 105 is formed is disposed between the wiring board 120 and the semiconductor chip 101, and the wiring board 120 and the semiconductor chip 101 are electrically connected via the rewiring layer 105. It is connected. As the insulating layer 115, the photosensitive resin composition layer (cured film) after the curing step 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 for 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 chip 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to a surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110a is formed between the insulating layer 115 and the semiconductor chip 101. An underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

  FIG. 2 is a schematic view showing a configuration of an embodiment of a laminate obtained by the method for producing a laminate of the present invention. FIG. 2 specifically shows an example in which a laminate obtained by the method for producing a laminate of the present invention is used as a rewiring layer. In FIG. 2, reference numeral 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 oblique lines. The photosensitive resin composition layer 201 is formed in a desired pattern by negative development. The metal layer 203 is formed so as to cover a part of the surface of the pattern, and a photosensitive resin composition layer (cured film) 201 is further laminated on the surface of the metal layer 203. Then, the photosensitive resin composition layer (cured film) functions as an insulating layer, the metal layer functions as a redistribution layer, and is incorporated in the above-described semiconductor element as a redistribution layer.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. “Parts” and “%” are based on mass unless otherwise specified.

[Example 1]
<Synthesis of polyimide precursor>
<< Synthesis of polyimide precursor Aa-1 (polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate >>
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic dianhydride (4,4′-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed. The mixture was stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes keeping the temperature at −10 ± 4 ° C. After diluting the reaction mixture 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 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The reaction mixture was then added into 5 liters of water to precipitate the polyimide precursor. The mixture of water and the 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 a polyimide precursor Aa-1.
The structure of the polyimide precursor Aa-1 is shown below.

<Preparation of photosensitive resin composition>
The following components were mixed to prepare a photosensitive resin composition 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 part by mass Polymerization inhibitor: 2,6-di-tert-butyl- 4-Methylphenol (Tokyo Kasei Kogyo): 0.1 parts by mass Migration inhibitor: 1H-1,2,4-triazole (Tokyo Kasei Kogyo): 0.1 parts by mass Solvent: γ-butyrolactone 48.00 parts by mass Part solvent: dimethyl sulfoxide 12.00 parts by mass

<< 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 part by mass Thermal base generator A-23 0.5 part by mass Polymerization prohibited Agent: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry): 0.1 part by mass Migration inhibitor: 1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry): 0. 1 part by weight solvent: γ-butyrolactone 48.00 parts by weight Solvent: dimethyl sulfoxide 12.00 parts by weight

Details of each additive are as follows.
Polymerizable compound B-1: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, structure shown below)

(C) Photopolymerization initiator C-1: Compound 24 described in paragraph 0345 of JP-A-2014-500852

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

<Photosensitive resin composition layer forming step>
Thereafter, each photosensitive resin composition was applied on a silicon wafer by spin coating to form a layer, thereby forming a photosensitive resin composition layer.

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

<Exposure process>
Next, the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm (i-line) and an exposure energy of 500 mJ / cm ² (uniform irradiation over the entire surface). .
In this embodiment, in order to easily measure the stress, the entire surface is exposed by uniform irradiation, immersed in a developer, and subjected to a curing step to form a cured film. However, a pattern-exposed cured film may be formed through a curing step by exposing to a pattern and immersing it in a developer to remove unexposed portions.
In the case where the photosensitive resin composition layer is patterned, more interfaces are generated than in the case where no patterning is performed, and a portion where the contact area is smaller between the substrate, the cured film and the metal layer when the metal layer is laminated. In this case, delamination is more likely to occur, and the effect of the present invention is more remarkably obtained.

<Development process>
The photosensitive resin composition layer that had been entirely exposed was immersed in cyclopentanone for 60 seconds and developed.

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

<< (1) Temperature rise process >>
First, a substrate having a photosensitive resin composition layer after development processing is placed on a temperature-adjustable plate under a nitrogen atmosphere having an oxygen concentration of 20 vol ppm or less, and the temperature is raised from room temperature (20 ° C.) by 10 ° C./min. The temperature was raised at a heating rate, and the mixture was heated to a final temperature of 230 ° C. over 21 minutes.

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

<< (3) Cooling process >>
After heating for 3 hours in the holding step, the photosensitive resin composition layer was slowly cooled from 230 ° C. to a final temperature of 170 ° C. in the cooling step over a period of 30 minutes at a rate of 2 ° C./min.

<< (4) Step of bringing to room temperature >>
After the photosensitive resin composition layer reached the final temperature of 170 ° C. in the cooling step, the photosensitive resin composition layer was cooled at a temperature lowering rate of 5 to 10 ° C./min to room temperature to obtain a cured film. .

<Characteristics of cured film>
<< Measurement of glass transition temperature >>
The glass transition temperature of the photosensitive resin composition layer (cured film) after the curing step was measured by the following method.
It was set in a dynamic viscoelasticity measuring apparatus, and the temperature was raised from 0 ° C. to 350 ° C. at a temperature rising rate of 10 ° C./min at a frequency of 1 Hz by a tension method, and Tg was determined from the peak temperature of tan δ.
The obtained results are shown in Table 1 below.
Table 1 below shows the difference between the glass transition temperature of the photosensitive resin composition layer (cured film) after the curing step and the ultimate temperature of the cooling step.

<< Stress measurement >>
The stress of the photosensitive resin composition layer (cured film) after the curing step was measured by the following method.
With respect to the silicon wafer before applying the photosensitive resin composition layer, the wafer was set in a thin film stress measuring device, and laser scanning was performed at room temperature to obtain a blank value.
The wafer on which the photosensitive resin composition layer (cured film) after the metal layer forming step and the second metal layer forming step is formed is set in a thin film stress measuring apparatus, and the photosensitive resin composition layer is subjected to laser scanning at room temperature. The stress was measured from the film thickness and the radius of curvature in comparison with the blank value before the application of the.
The obtained results are shown in Table 1 below.

<Metal layer forming step>
Next, on the photosensitive resin composition layer after the curing step, a first metal layer to be used as a barrier metal film by forming a film of Ti to a thickness of 100 nm by a sputtering method, and then continuously forming Cu to a thickness of 300 nm. The film was formed to form a seed layer.

<Second metal layer forming step>
Next, a dry film resist (Photec RY-3525, manufactured by Hitachi Chemical Co., Ltd.) is adhered on the seed layer with a roll laminator, and a photo tool on which a pattern is formed is brought into close contact with the seed layer, and EXM-1201 manufactured by Oak Manufacturing Co., Ltd. Exposure was performed with an energy amount of 100 mJ / cm ² using a mold exposure machine. Next, spray development was performed for 90 seconds with a 1% by mass aqueous solution of sodium carbonate at 30 ° C. to open the dry film resist. Next, a copper plating layer having a thickness of 7 μm was formed on the dry film resist and on the seed layer in the portion where the dry film resist was opened by using an electrolytic copper plating method. Next, the dry film resist was stripped using a stripping solution. Next, the portion of the seed layer from which the dry film resist had been removed was removed using an etchant to form a patterned metal layer on the surface of the photosensitive resin composition layer after the curing step.

<Lamination process>
Further, on the surface where the unevenness is formed by the metal layer and the photosensitive resin composition layer after the curing step, the photosensitive resin composition is cured from the filtration step of the photosensitive resin composition in the same manner as above using the same photosensitive resin composition again. The procedure up to the step was performed again to form a laminate having two photosensitive resin composition layers after the curing step.
Further, the metal layer forming step was performed again on the laminate having two photosensitive resin composition layers after the curing step in the same manner as above to form a laminate.

[Examples 2 to 4 and Comparative Examples 1 to 4]
Except having changed to the conditions shown in the following table, it carried out similarly to Example 1, and manufactured the cured film and laminated body of Examples 2-4 and Comparative Examples 1-4.
About the obtained cured film, the characteristic of the cured film was evaluated in the same manner as in Example 1.

From Table 1 above, it was found that the residual stress of the cured film can be greatly reduced by setting the temperature drop rate in the cooling step to 2 ° C./min or less. By reducing the residual stress of the cured film, warping of the substrate when the substrate and the cured film are stacked can be suppressed. In addition, delamination in the laminate of the cured film and the metal layer can also be suppressed. Furthermore, when two or more sets of a cured film and a metal layer are laminated, delamination can also be suppressed.
On the other hand, from Comparative Examples 1 to 4, it was found that when the cooling rate in the cooling step was larger than the range specified in the present invention, the residual stress of the cured film was large. When the residual stress of the cured film is large, the warpage of the substrate when the substrate and the cured film are laminated increases. In addition, delamination in the laminated body of the cured film and the metal layer is likely to occur.

In Example 1, the metal layer (copper thin film) was changed to an aluminum thin film, and the other steps were performed in the same manner. As a result, good results were obtained as in Example 1.
In Example 1, the solid content concentration of the photosensitive resin composition 1 was reduced to 1/10 without changing the composition ratio, and spray coating was performed using a spray gun ("NanoSpray" manufactured by EV Group (EVG), Austria). Then, a laminate was formed in the same manner as in Example 1. The same excellent effects as in Example 1 were obtained.
In the production of the laminate of Example 1, a laminate was produced in the same manner as in Example 1 except that heating (pretreatment) at 100 ° C. for 10 minutes was performed before heating at 230 ° C. for 3 hours. The properties were evaluated. Excellent effects were obtained in the same manner as in Example 1.
In the production of the laminate of Example 1, a laminate was produced in the same manner as in Example 1 except that heating (pretreatment) at 150 ° C. for 10 minutes was performed before heating at 230 ° C. for 3 hours. The properties were evaluated. Excellent effects were obtained in the same manner as in Example 1.
In the manufacture of the laminate of Example 1, the same procedure as in Example 1 was performed, except that heating (pretreatment) at 180 ° C. for 10 minutes was performed while irradiating UV light before heating at 230 ° C. for 3 hours. Laminates were manufactured and properties were evaluated. Excellent effects were obtained in the same manner as in Example 1.

  Since the cured film produced by the method for producing a cured film of the present invention has a small residual stress, warpage of the substrate when the substrate and the cured film are laminated can be suppressed. In the laminate manufactured by the method for manufacturing a laminate of the present invention, delamination in a laminate of a substrate, a cured film, and a metal layer can also be suppressed. Furthermore, in the laminate manufactured by the method for manufacturing a laminate of the present invention, delamination can be suppressed even when two or more sets of a laminate of a substrate, a cured film, and a metal layer are laminated. Such a laminate can be used to manufacture an interlayer insulating layer for a redistribution layer of a semiconductor element, and can provide an interlayer insulating layer for a redistribution layer in which delamination is suppressed. In addition, such a laminate is used for producing an interlayer insulating layer for power semiconductors, a copper pillar middle film or a single-layer insulating layer for three-dimensional integrated circuits (IC), and an interlayer insulating layer for panels. Available.

100: semiconductor elements 101, 101a to 101d: semiconductor chips 102b, 102c, 102d: through electrodes 103a to 103e: metal bump 105: redistribution layers 110, 110a, 110b: underfill layer 115: insulating layer 120: wiring board 120a: Surface electrode 200: laminate 201: photosensitive resin composition layer (cured film)
203: metal layer

Claims (11)

A photosensitive resin composition comprising a polyimide precursor having an unsaturated bond, a polymerizable compound having two or three unsaturated bonds, and a photosensitive resin composition containing a photopolymerization initiator applied to a substrate to form a layer. Material layer forming step,
An exposure step of exposing the photosensitive resin composition layer is the photosensitive resin composition which is layered,
A developing process of performing a developing process on the exposed photosensitive resin composition layer,
A curing step of curing the photosensitive resin composition layer after the development processing,
In the above order,
The curing step,
A temperature raising step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature of the photosensitive resin composition layer after the curing step ;
A cooling step of cooling the photosensitive resin composition layer to a temperature lower than the glass transition temperature by 30 ° C. or more at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.   The method for producing a cured film according to claim 1, further comprising a holding step of holding the holding temperature equal to the final temperature of the heating step for at least 30 minutes after the heating step and before the cooling step.   The method for producing a cured film according to claim 2, wherein the holding temperature in the holding step is 150 to 450C. The method for producing a cured film according to any one of claims 1 to 3 , wherein a time of the cooling step is longer than a time of the temperature raising step. The method for producing a cured film according to any one of claims 1 to 4 , wherein a residual stress of the photosensitive resin composition layer after the curing step, measured according to a laser measurement method, is less than 35 MPa. The method for producing a cured film according to any one of claims 1 to 5 , wherein the photosensitive resin composition is for negative tone development. The method for producing a cured film according to any one of claims 1 to 6 , wherein the photosensitive resin composition forms a crosslinked structure upon exposure to light, and decreases the solubility in an organic solvent. Including a method for producing a cured film according to any one of claims 1 to 7 ,
A method for producing a laminate, further comprising a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step. The method for producing a laminate according to claim 8, wherein the photosensitive resin composition layer forming step, the exposing step, the developing step, and the curing step are performed again in the above order. The method according to claim 8 or 9 , wherein the photosensitive resin composition layer forming step, the exposing step, the developing step, the curing step, the heating step, the cooling step, and the metal layer forming step are performed again in the above order. A method for producing the laminate according to the above. A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to claim 8 .

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