JP7478806B2 - Organic film and its manufacturing method, composition, laminate, and semiconductor device - Google Patents

Description

The present invention relates to an organic film and its manufacturing method, a composition, a laminate, and a semiconductor device.

The organic film can be formed by using an easy film formation method such as a coating method, a printing method, a transfer method, etc. In addition, by adjusting the structure of each component (e.g., resin, etc.) contained in the film, the content of each component contained in the film, etc., it is also possible to easily design the mechanical properties of the film, such as breaking elongation, and the physical properties of the film, such as insulating properties, etc. For this reason, in recent years, organic films containing organic materials have been used in various fields as films used in devices for various purposes.
For example, organic films containing resins such as polyimide and benzoxazole have excellent heat resistance and insulating properties and are therefore used in a variety of applications. The applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, they can be used as insulating films, sealing materials, or protective films. They are also used as base films or coverlays for flexible substrates.
There are high expectations for the industrial application of such organic films.

For example, Patent Document 1 describes a photosensitive resin composition that contains component (A), which is a photosensitive polyimide precursor, and component (B), which has a specific structure.

International Publication No. 2017/033833

As organic films are used in a variety of fields, there is a demand for organic films that have excellent solvent resistance.

The present invention aims to provide an organic film having excellent solvent resistance and a method for producing the same, a composition used to form the organic film, a laminate including the organic film, and a semiconductor device including the organic film or the laminate.

Representative embodiments of the present invention will be described below.
<1> An organic film satisfying at least one formula selected from the group consisting of the following formula (1) and the following formula (2):
Formula (1): I / A ≧ 2.5
Formula (2): I / B ≧ 0.5
In the above formula (1) or (2), I is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 , A is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.200 Å ^-1 to 0.300 Å ^-1 , B is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.017 Å ^-1 to 0.025 Å ^-1 , and q is a value defined by the following formula (Q) in small-angle scattering:
Formula (Q): q = (4π/λ) sin θ
In formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam.
<2> The organic film according to <1>, which is a cured product of a coating film of a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor, and a polybenzoxazole precursor.
<3> The organic film according to <2>, wherein the composition contains a photosensitizer.
<4> A composition for forming an organic film according to any one of <1> to <3>.
<5> A laminate comprising two or more layers of the organic film according to any one of <1> to <3>, and a metal layer between any two adjacent layers of the organic films.
<6> A semiconductor device comprising the organic film according to any one of <1> to <3> or the laminate according to <5>.
<7> A method for producing the organic film according to any one of <1> to <3>, comprising a film formation step of applying a composition to a substrate to form a film.
<8> The method for producing an organic film according to <7>, further comprising the step of heating the film at 50 to 450° C.

The present invention provides an organic film having excellent solvent resistance and a method for producing the same, a composition used to form the organic film, a laminate including the organic film, and a semiconductor device including the organic film or the laminate.

The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower limit and upper limit, respectively.
In this specification, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from another step, so long as the intended effect of the step can be achieved.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and actinic rays or radiation such as electron beams.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise stated. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, these molecular weights were measured using THF (tetrahydrofuran) as the eluent. In addition, the detection in the GPC measurement was performed using a UV (ultraviolet) wavelength 254 nm detector, unless otherwise stated.
In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a composition layer, the direction from the substrate to the composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise stated, the temperature is 23° C. and the pressure is 101,325 Pa (1 atm).
As used herein, combinations of preferred aspects are more preferred aspects.

(Organic film)
The organic film of the present invention satisfies at least one formula selected from the group consisting of the following formula (1) and the following formula (2).
Formula (1): I / A ≧ 2.5
Formula (2): I / B ≧ 0.5
In the above formula (1) or (2), I is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 , A is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.200 Å ^-1 to 0.300 Å ^-1 , B is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.017 Å ^-1 to 0.025 Å ^-1 , and q is a value defined by the following formula (Q) in small-angle scattering.
Formula (Q): q = (4π/λ) sin θ
In formula (Q), λ is the wavelength of the neutron beam (Å), and θ is the scattering angle of the neutron beam (°).
Also, 1 Å is 0.1 nm.

The organic film of the present invention has excellent solvent resistance.
According to the present invention, it is believed that an organic film having excellent solvent resistance, in which solubility in polar solvents such as dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP) is suppressed, is provided.
An organic film having excellent solvent resistance is considered to be useful, for example, when used in a product that may come into contact with a solvent during use, storage, or production, when a composition containing a solvent is further applied onto the organic film, or when a film formed on the organic film is subjected to solvent development, because dissolution of the organic film in a solvent is suppressed.

The reason why the organic film of the present invention has excellent solvent resistance is not clear, but is presumed to be as follows.
Satisfying formula (1) means that the maximum relative intensity value I when small-angle neutron scattering measurement is performed with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 is 2.5 times or more the minimum relative intensity value A when small-angle neutron scattering measurement is performed with q in the range of 0.200 Å ^-1 to 0.300 Å ^-1 .
Satisfying the formula (2) means that the maximum value I is 0.5 or more times the minimum value B of the relative intensity value when small-angle neutron scattering measurement is performed with q in the range of 0.017 Å ^-1 to 0.025 Å ^-1 .
As a result of intensive research, the present inventors have found that an organic film in which the maximum value I in the range of q from 0.030 Å ⁻¹ to 0.065 Å ⁻¹ is 2.5 times or more than the minimum value A, or 0.5 times or more than the minimum value B, or which satisfies both, has excellent solvent resistance.
Here, the maximum value I of the relative intensity when small-angle neutron scattering measurement is performed with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 is considered to be a value that changes depending on the arrangement and association state of the components such as the resin contained in the organic film.
As an example, when the organic film contains a resin having a ring structure (e.g., a heterocyclic structure) such as a polyimide resin, for example, when the organic film contains many stacked ring structures, the maximum value I increases and it is considered that at least one selected from the group consisting of the above-mentioned formula (1) and formula (2) is satisfied.
In addition, for example, when the organic film contains a large amount of the above-mentioned ring structures stacked together, the interaction between the resins is strong, or the density of the resin in the organic film is biased, and there are parts in the organic film with high resin density, and for these reasons, the organic film is considered to have excellent solvent resistance.
Based on the above findings, the present inventors have found that an organic film having excellent solvent resistance can be obtained by making the organic film satisfy at least one formula selected from the group consisting of formula (1) and formula (2), and have completed the present invention.
In addition, due to the interaction between the resins and the like, it is considered that when the organic film satisfies at least one formula selected from the group consisting of formula (1) and formula (2), an organic film having large breaking elongation and excellent mechanical properties is easily obtained.

<Small angle neutron scattering (SANS) measurement>
The small angle neutron scattering measurement is carried out by the method described in the Examples below.
In addition, the relative intensity value in the present invention is a value obtained by subtracting the background count number measured using a blank cell containing no sample (e.g., an empty sample holder not filled with a measurement sample) from the count number measured by performing small-angle neutron scattering measurement on a measurement sample.

The organic film of the present invention may satisfy at least one formula selected from the group consisting of formula (1) and formula (2), but it is also a preferred embodiment that the organic film satisfies both formula (1) and formula (2).

[I/A]
The value of I/A described in formula (1) is 2.5 or more, preferably 2.6 or more, more preferably 2.7 or more, even more preferably 2.8 or more, still more preferably 3.0 or more, particularly preferably 4.0 or more, and most preferably 4.2 or more.
The upper limit of the I/A value is not particularly limited, but may be, for example, 100 or less.
The value of I/A is considered to be determined by, for example, the structure of the resin contained in the organic film, the structure of the components other than the resin contained in the organic film, the combination of components having a specific structure, the content of each component contained in the organic film, the manufacturing method of the organic film (e.g., the curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, etc.

[I/B]
The value of I/B described in formula (2) is 0.5 or more, preferably 0.55 or more, more preferably 0.60 or more, even more preferably 0.65 or more, still more preferably 0.70 or more, particularly preferably 0.80 or more, and most preferably 0.84 or more.
The upper limit of the I/B value is not particularly limited, but may be, for example, 20 or less.
The value of I/B is considered to be determined by, for example, the structure of the resin contained in the organic film, the structure of the components other than the resin contained in the organic film, the combination of components having a specific structure, the content of each component contained in the organic film, the manufacturing method of the organic film (e.g., the curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, etc.

[Maximum value I]
The maximum value I when q is in the range of 0.030 Å ⁻¹ to 0.065 ^{Å −1} may be within the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ , but it is preferable that the maximum value I be within the range of q of 0.032 Å −1 to 0.065 Å ⁻¹ , and it is more preferable that the maximum value I be within the range of q of 0.034 Å ⁻¹ to 0.065 Å ⁻¹ .

[ ^I12 /A, ^I13 /A]
When the organic film of the present invention satisfies formula (1), it preferably further satisfies the following formula (1-2), and more preferably further satisfies the following formula (1-3).
Formula (1-2): I ¹² /A≧2.5
Formula (1-3): I ¹³ /A≧2.5
In the above formula (1-2) or (1-3), ^I12 is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.035 Å ^-1 to 0.065 Å ^-1 , ^I13 is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.040 Å ^-1 to 0.065 Å ^-1 , and A and q are defined as A and q in formula (1).

[ ^I22 /B, ^I23 /B]
When the organic film of the present invention satisfies the formula (2), it preferably further satisfies the following formula (2-2), and more preferably further satisfies the following formula (2-3).
Formula (2-2): I ²² /B≧0.5
Formula (2-3): I ²³ /B≧0.5
In the above formula (1-2) or (1-3), ^I22 is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.035 ^Å- 1 to 0.065 Å ^- 1, ^I23 is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.040 Å ^-1 to 0.065 Å ^-1 , and B and q are defined as A and q in formula (2).

<Ingredients>
The organic film of the present invention may be any film containing an organic component, but is preferably a film containing a resin.
The resin is preferably a resin having a ring structure, more preferably a resin having a heterocyclic structure.
Furthermore, the resin is not particularly limited, and examples thereof include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polysiloxane, resins containing a siloxane structure, epoxy resin, (meth)acrylic resin, olefin-based resins such as polyethylene and polypropylene, vinyl-based resins such as polyvinyl chloride and polyvinyl ester, polyurethane, polyurea, polyamide, polycarbonate, polyester, polystyrene, polyacetal, cellulose resin, phenol resin, and fluorine-based resins such as polytetrafluoroethylene.
Among these, from the viewpoint of the insulating property and heat resistance of the organic film, the organic film preferably contains polyimide or polybenzoxazole as the resin, and more preferably contains polyimide.
The polyimide or polybenzoxazole is preferably a polyimide contained in a composition described later, a polybenzoxazole contained in a composition described later, a polyimide formed from a polyimide precursor contained in a composition described later, or a polybenzoxazole formed from a polybenzoxazole precursor contained in a composition described later.
The organic film may further contain, as other components, each component contained in the composition described later. In addition, when the organic film is obtained by reacting at least one of the components in the composition, for example, forming the organic film as a cured product, each component (e.g., photopolymerization initiator, polymerizable compound, etc.) contained in the composition described later may be contained in a form after reaction (e.g., photopolymerization initiator after exposure, polymerizable compound after polymerization, etc.).

The organic film is preferably an organic film formed from a coating film of a composition, more preferably a cured product of a coating film of a composition, even more preferably a cured product of a coating film of a composition containing the above-mentioned resin, and particularly preferably a cured product of a coating film of a composition containing at least one resin (hereinafter also referred to as a "specific resin") selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.
Each component contained in the composition will be described below.

<Resin>
Examples of the resin contained in the composition include the resin contained in the organic film described above, or a resin that will become the resin contained in the organic film described above in the cured product. The resin is preferably at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, more preferably at least one resin selected from the group consisting of polyimide and polyimide precursor, and even more preferably a polyimide precursor.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in terms of its type, but it preferably contains a repeating unit represented by the following formula (2).
Equation (2)

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, and preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. 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 consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. A particularly preferred embodiment of the present invention is exemplified by a group represented by -Ar-L-Ar-. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, or NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, it is preferable that the diamine contains 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 consisting of a combination thereof, and it is more preferable that the diamine contains a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.

In the formula, A is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, NHCO-, or a group selected from these combinations, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ₂ -, and further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-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; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diamino Biphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxyphenyl)propane, -4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 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'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoxyethyl Anamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl) 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]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)phenyl At least one diamine selected from 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(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, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

The diamines (DA-1) to (DA-18) shown below are also preferred.

Also preferred are diamines having at least two alkylene glycol units in the main chain. More preferred are diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferred are diamines that do not contain aromatic rings. Specific examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like, but are not limited thereto.
The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

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

From the viewpoint of flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61).
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, a methyl group, or a trifluoromethyl group.
Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom or a trifluoromethyl group.
Examples of diamine compounds that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

In formula (2), R ¹¹⁵ 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 formula (6) is more preferable.
Equation (5)

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

Equation (6)

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of an anhydride group from a tetracarboxylic dianhydride, etc. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Formula (O)
In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2,2 ',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic 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-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyl tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

Further, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) are also preferred examples.

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ may be a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a photoradical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group. As the radical polymerizable group of the polyimide precursor or the like, 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), with the group represented by the following formula (III) being preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group, of which an ethylene group, a propylene group, a trimethylene group, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group are more preferred, and from the viewpoint of making it easier to satisfy formula (1) or formula (2) in the organic film, a polyalkyleneoxy group is even more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy groups in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aromatic groups and aralkyl groups in which an acidic group is bonded to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples include aromatic groups having 6 to 20 carbon atoms and having an acidic group, and aralkyl groups having 7 to 25 carbon atoms and having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ 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, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups 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, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a campholoyl group, a dicyclohexyl group, and a pinenyl group. Among them, the cyclohexyl group is the most preferable from the viewpoint of compatibility with high sensitivity. In addition, the alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group as described below.
Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, A pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring. A benzene ring is most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

It is also preferable that the polyimide precursor has fluorine atoms in the structural units. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 20% by mass or less.

In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By adopting such a structure, it is possible to further widen the width of the exposure latitude.
Formula (2-A)

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same definition as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same.
R ¹¹² has the same definition as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating structural unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of formula (2).

One embodiment of the polyimide precursor in the present invention is a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of the total repeating units are repeating units represented by formula (2).

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 even more preferably 22,000 to 25,000. When the organic film-forming composition of the present invention contains a metal element-containing compound, an embodiment in which the weight average molecular weight (Mw) is 22,000 to 26,000 is also preferred. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. When the organic film-forming composition of the present invention contains a metal element-containing compound, an embodiment in which the number average molecular weight (Mn) is 7,200 to 20,000 is also preferred, and in that case, the number average molecular weight (Mn) is more preferably 8,000 to 18,000, and even more preferably 10,000 to 14,000.
The molecular weight 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. When the organic film-forming composition of the present invention contains a metal element-containing compound, the molecular weight dispersity is preferably 1.5 or more, and in this case, it is more preferably 1.7 or more, and even more preferably 1.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3.8 or less, even more preferably 3.2 or less, even more preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In this specification, the term "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to any other bonding chain.

-Fluorine atom-
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably contains fluorine atoms.
The fluorine atom is preferably contained, for example, in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably from 1 to 50 mol/g, and more preferably from 5 to 30 mol/g.

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide contains a silicon atom.
The silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably contained in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³¹ in the repeating unit represented by formula (4) described later.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and preferably a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.

Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents a bonding site with the oxygen atom to which R ²⁰¹ in formula (III) is bonded.
In formulas (R1) to (R3), preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for L are the same as the preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for ^R21 described above.
In formula (R1), X is preferably an oxygen atom.
In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

In formula (IV), * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

- Crosslinkable group other than ethylenically unsaturated bond -
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of crosslinkable groups other than ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
A crosslinkable group other than an ethylenically unsaturated bond is preferably contained in, for example, R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

-Acid value-
When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably from 2 to 35 mgKOH/g, more preferably from 3 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, the value listed in "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced.
Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained, for example, in R ¹³² in the repeating unit represented by formula (4) described below, or in R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide ring, but it preferably contains a repeating unit represented by the following formula (4), and more preferably is a compound containing a repeating unit represented by formula (4) and having a polymerizable group.
Equation (4)

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

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are the same as those in formula (4).
Formula (4-2)

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

The polymerizable group has the same meaning as the polymerizable group described above in relation to the polymerizable group contained in the polyimide precursor or the like.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same as those of R ¹¹¹ in formula (2), and the preferred range is also the same.
R ¹³¹ may be a diamine residue remaining after removal of the amino group of the diamine. The diamine may be an aliphatic, cyclic aliphatic, or aromatic diamine. Specific examples include the example of R ¹¹¹ in the formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue not containing an aromatic ring.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same as those of R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, the four bonds of the tetravalent organic group exemplified as R ¹¹⁵ bond to the four —C(═O)— portions in the above formula (4) to form a condensed ring.

Furthermore, R ¹³² may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. A specific example is R ¹¹⁵ in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, preferred examples of R ¹³¹ include 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, and the above (DA-1) to (DA-18), and more preferred examples of R ¹³² include the above (DAA-1) to (DAA-5).

It is also preferable that the polyimide has fluorine atoms in its structural units. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and 20% by mass or less.

In order to improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

In addition, in order to improve the storage stability of the composition, it is preferable to cap the main chain ends of the polyimide with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Of these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents.

-Imidization rate (ring closure rate)-
From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula.
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

The polyimide may contain repeating structural units of the above formula (4) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (4) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyimide may contain other types of repeating structural units in addition to the repeating units of the above formula (4).

Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent which is a monoamine) at low temperature, by reacting a tetracarboxylic dianhydride (partially substituted with a terminal blocking agent which is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with a diamine compound at low temperature, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a terminal blocking agent which is a monoamine) in the presence of a condensing agent, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a terminal blocking agent which is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized by a known imidization reaction method, or by stopping the imidization reaction midway and partially introducing an imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when two or more types of polyimides are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is in the above range.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)

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

In formula (3), R ¹²³ and R ¹²⁴ each have the same definition as R ¹¹³ in formula (2), and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids 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, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

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

As dicarboxylic acids containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only an aromatic group and two -COOH groups are more preferred.

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

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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-4-hydroxyphenyl)hexafluoropropane, and the like. Examples of the bisaminophenols include 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

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

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

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). 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. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R ₃ , is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and is particularly preferred in that the effect of achieving a high cyclization rate when cured at a low temperature is further enhanced.

In addition, in the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group, since this can maintain the effects of high transparency to i-line and a high cyclization rate when cured at a low temperature.

In the above formula (As), it is more preferable that R ₁ is an alkylene or a substituted alkylene. Specific examples of alkylene and substituted alkylene for 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 _{( CH3 )} ( _CH2CH ( _CH3 ) ₂ ) _- , -CH ₍ CH2CH2CH2CH2CH2CH3 _{) -} , -C( _CH3 )(CH2CH2CH2CH2CH2CH3) _- , _{-CH ( CH2CH2CH2CH2CH2CH2CH3)-, -C(CH3 ) ( CH2CH2CH2CH2CH2CH2CH3 ) - , -CH ( CH2CH2CH2CH2CH2CH2CH3} )-, -C( _CH3 ) _{( CH2CH2CH2CH2CH2CH2CH3} )- and the like. Among these, _-CH2- , -CH( _CH3 )- and -C( _{CH3 ) 2-} are more preferred in that they are capable of providing a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

For the production method of the bisaminophenol derivative represented by the above formula (A-s), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Needless to say, the invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of formula (3) above.
In terms of being able to suppress the occurrence of warping due to ring closure, it is preferable that the resin composition contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

In 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, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. 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, 95 to 5 mol % for the b-structure, and a+b is 100 mol %.

In formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

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

When used in a composition described later, the polybenzoxazole precursor has a weight average molecular weight (Mw) of preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring. However, it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group.

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

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

In formula (X-2), R ¹³⁷ is a polymerizable group, and the others are substituents, and the other groups are the same as defined in formula (X).

The polymerizable group has the same meaning as the polymerizable group described above in relation to the polymerizable group possessed by the polyimide precursor, etc.

R ¹³³ represents a divalent organic group. The divalent organic group may be an aliphatic or aromatic group. Specific examples include the examples of R ¹²¹ in the formula (3) of the polybenzoxazole precursor. In addition, preferred examples thereof are the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include the examples of R ¹²² in the formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R ¹²² .
For example, the four bonds of the tetravalent organic group exemplified as R ¹²² bond to the nitrogen atom and 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 oxazolization rate of 85% or more, and more preferably 90% or more. By having an oxazolization rate of 85% or more, the film shrinkage caused by ring closure that occurs when the film is oxazolized by heating is reduced, and warping can be more effectively suppressed.

The polybenzoxazole may contain repeating structural units of the above formula (X) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (X) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating units of the above formula (X).

Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method.
In the case of dicarboxylic acids, in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative which has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole or the like.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, 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 in the above range.

[Method for producing polyimide precursors, etc.]
The polyimide precursor or the like can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine, preferably by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the halogenated dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
In the method for producing a polyimide precursor or the like, 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 selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (e.g., promoting the cyclization reaction by the action of a catalyst), or the polyimide may be synthesized directly.

-End-capping agent-
In the method for producing a polyimide precursor or the like, in order to further improve storage stability, it is preferable to cap the ends of the polyimide precursor or the like with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. As the end-capping agent, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-9-aminonaphthalene, 1-carboxy-10-aminonaphthalene, 1-carboxy-11-aminonaphthalene, 1-carboxy-12-aminonaphthalene, 1-carboxy-13-aminonaphthalene, 1-carboxy-14-aminonaphthalene, 1-carboxy-15-aminonaphthalene, 1-carboxy-16-aminonaphthalene, 1-carboxy-17-aminonaphthalene, 1-carboxy-18-aminonaphthalene, 1-carboxy-19 ... Examples of the amino acid include 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. 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.

-Solid precipitation-
The production of the polyimide precursor or the like may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and then dissolved in a solvent in which the polyimide precursor or the like is soluble, such as tetrahydrofuran, to precipitate the solid.
Thereafter, the polyimide precursor or the like is dried to obtain a powdered polyimide precursor or the like.

〔Content〕
The content of the resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the composition. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the composition.
The composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

<Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, simply referred to as "another resin") different from the specific resin.
Examples of the other resin include polyimides different from the specific resin, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.
For example, by further adding an acrylic resin, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained.
For example, by adding an acrylic resin having a weight-average molecular weight of 20,000 or less and a high polymerizable group value to the composition in place of or in addition to the polymerizable compound described later, the coatability of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the composition.
In addition, the content of other resins in the composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, even more preferably 70 mass % or less, still more preferably 60 mass % or less, and even more preferably 50 mass % or less, based on the total solid content of the composition.
In addition, as a preferred embodiment of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitizer.
The photosensitizer is preferably a photopolymerization initiator.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

From the viewpoint of making it easier for the organic film to satisfy at least one formula selected from the group consisting of the above formula (1) and formula (2), the composition of the present invention preferably contains a metal element-containing compound described later as a photoradical polymerization initiator. That is, in the present invention, among the metal element-containing compounds described later, one having radical polymerization initiation ability can be used as a photoradical polymerization initiator.
Here, having radical polymerization initiation ability means that it can generate free radicals that can initiate radical polymerization. For example, when a composition containing a radical polymerizable monomer, a binder polymer, and a metal element-containing compound is irradiated with light in a wavelength range in which the metal element-containing compound absorbs light and the radical polymerizable monomer does not absorb light, the presence or absence of polymerization initiation ability can be confirmed by checking whether or not the radical polymerizable monomer disappears. To check whether or not it disappears, an appropriate method can be selected depending on the type of radical polymerizable monomer or binder polymer, and it can be confirmed by, for example, IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography).

When the composition of the present invention contains a metal element-containing compound having radical polymerization initiation ability, it is also preferable that the composition of the present invention does not substantially contain any radical polymerization initiator other than the metal element-containing compound. The term "substantially does not contain any radical polymerization initiator other than the metal element-containing compound" means that the content of the radical polymerization initiator other than the metal element-containing compound in the composition of the present invention is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass, based on the total mass of the metal element-containing compound.
In addition, when the composition of the present invention contains a metal element-containing compound having radical polymerization initiation ability, it is also preferable that the composition of the present invention contains the above-mentioned metal element-containing compound and another photoradical polymerization initiator.
In the composition of the present invention, when the composition contains a metal element-containing compound and another photoradical polymerization initiator, the content of the metal element-containing compound relative to the total content of the metal element-containing compound and the other photoradical polymerization initiator is preferably 20 to 80 mass%, and more preferably 30 to 70 mass%.
As the other photoradical polymerization initiator, an oxime compound described below is preferable.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219 A, the contents of which are incorporated herein by reference.

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

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

Hydroxyacetophenone initiators that can be used include IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF).

As aminoacetophenone initiators, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF) can be used.

As an aminoacetophenone initiator, the compounds described in JP 2009-191179 A, which have a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can also be used.

Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF). Metallocene compounds include compounds containing metal elements, as described below, that have the ability to initiate radical polymerization.

As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of oxime compounds that can be used include the compounds described in JP-A-2001-233842, JP-A-2000-080068, and JP-A-2006-342166.

Preferred oxime compounds include, for example, compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-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. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitably used. TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-831 and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito ChemiX Co., Ltd.) can also be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

The most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having thioaryl groups as disclosed in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole 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.

More preferred photoradical polymerization 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, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, with metallocene compounds or oxime compounds being even more preferred, and oxime compounds being even more preferred.

As the photoradical polymerization initiator, benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketone such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, benzyl derivatives such as benzyl dimethyl ketal, etc. can also be used. Compounds represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, or a biphenyl; R ^I01 is a group represented by formula (II) or is the same group as R ^I00 ; and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

The photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of WO 2015/125469.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. When two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range.

[Photoacid generator]
The composition of the present invention also preferably contains a photoacid generator as a photosensitizer.
By including a photoacid generator, for example, an acid is generated in the exposed portion of the composition layer, which increases the solubility of the exposed portion in a developer (e.g., an alkaline aqueous solution), thereby obtaining a positive relief pattern in which the exposed portion is removed by the developer.
In addition, by containing a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed area promotes a crosslinking reaction of the polymerizable compound, and the exposed area becomes more difficult to remove with a developer than the non-exposed area. According to such an embodiment, a negative relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid upon exposure to light, but examples include quinone diazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Examples of quinone diazide compounds include polyhydroxy compounds to which sulfonic acid of quinone diazide is bonded via ester, polyamino compounds to which sulfonic acid of quinone diazide is bonded via sulfonamide, and polyhydroxy polyamino compounds to which sulfonic acid of quinone diazide is bonded via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol % or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide.

In the present invention, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used as the quinone diazide. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp, and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp, and are suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. In addition, naphthoquinone diazide sulfonyl ester compounds having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

The naphthoquinone diazide compound can be synthesized by esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. The use of these naphthoquinone diazide compounds improves the resolution, sensitivity, and film remaining rate.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts or esters of these compounds.

Examples of the onium salt compound or sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
Alternatively, commercially available photoacid generators may be used, such as WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 2 to 15% by mass, based on the total solid content of the composition of the present invention. Only one type of photoacid generator may be included, or two or more types may be included. When two or more types of photoacid generators are included, the total content is preferably within the above range.

<Metal element-containing compound>
The composition of the present invention preferably further contains a metal element-containing compound.
From the viewpoint of further improving the solvent resistance, the metal element-containing compound in the present invention is preferably the above-mentioned photoradical polymerization initiator.
The metal element-containing compound is preferably an organic substance containing a metal element, i.e., an organometallic compound.
In addition, examples of the metal element in the metal element-containing compound in the present invention include iron, palladium, nickel, and Group 4 elements, with Group 4 elements being preferred.
That is, the metal element-containing compound is preferably a Group 4 element-containing compound, and more preferably an organic Group 4 element-containing compound.
The Group 4 element-containing compound is preferably an organic compound containing at least one selected from the group consisting of titanium, zirconium and hafnium atoms, more preferably an organic compound containing at least one selected from the group consisting of titanium and zirconium atoms, and even more preferably an organic compound containing a titanium atom. The organic compound containing at least one selected from titanium and zirconium atoms is preferably an organic compound containing an organic group and a titanium or zirconium atom, and the number of titanium and zirconium atoms contained in one molecule of the organic compound is preferably one in total. The organic group is not particularly specified, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom.
In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are cyclic groups. The cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably selected from a 5-membered ring cyclic group. The 5-membered ring cyclic group is preferably a cyclopentadienyl group. In addition, the organotitanium compound used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
The Group 4 element-containing compound in the present invention is preferably a compound represented by the following formula (P).

In formula (P), M is a Group 4 element, and each R is independently a substituent.
It is preferable that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

As the Group 4 element represented by M, a titanium atom, a zirconium atom, and a hafnium atom are preferred, and a titanium atom and a zirconium atom are more preferred.

The aromatic group for R includes aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group.
The alkyl group for R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
The halogen atom in R includes F, Cl, Br and I.
The alkyl chain constituting the alkylsulfonyloxy group in R is preferably an alkyl chain having 1 to 20 carbon atoms, more preferably an alkyl chain having 1 to 10 carbon atoms, and examples thereof include a methyl chain, an ethyl chain, a propyl chain, an octyl chain, an isopropyl chain, a t-butyl chain, an isopentyl chain, a 2-ethylhexyl chain, a 2-methylhexyl chain, and a cyclopentyl chain.
The R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

The Group 4 element-containing compound used in the present invention preferably contains at least one selected from the group consisting of metallocenes and metallocene derivatives.
In the present invention, the metallocene derivative refers to an organometallic compound having two substituted cyclopentadienyl anion derivatives as η5-ligands, and includes titanocene derivatives, zirconocene derivatives, hafnocene derivatives, and the like.
The Group 4 element-containing compound used in the present invention is preferably selected from a titanocene compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound, and a hafnocene compound, more preferably from a titanocene compound, a zirconocene compound, and a hafnocene compound, and even more preferably from a titanocene compound and a zirconocene compound.
The Group 4 element-containing compound is preferably at least one selected from the group consisting of titanocene, titanocene derivatives, zirconocene, and zirconocene derivatives, and more preferably at least one selected from the group consisting of titanocene and titanocene derivatives.

The molecular weight of the Group 4 element-containing compound is preferably 50 to 2,000, more preferably 100 to 1,000.

Specific examples of the Group 4 element-containing compound include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, and the following compounds.

In addition, among the Group 4 element-containing compounds, examples of organic compounds containing titanium atoms include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5 ,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyr-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl-amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetylamino)phenyl]titanium, bis (cyclopentadienyl)bis[2,6-difluoro-3-(N-methylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylpropionylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(2,2-dimethylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-pentyl-(2,2-dimethylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-difluoro-3-(N-hexyl)-(2,2-dimethylbutanoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylcyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylisobutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetylamino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2,5,5-tetramethyl-1,2,5-azadichloridinyl-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-tolylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro Fluoro-3-(4-dodecylphenylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-(1-pentylheptyl)phenylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((4-bromophenyl)sulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-naphthylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(hexadecylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methyl-(4-dodecylphenyl)sulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-difluoro-3-(N-methyl-4-(1-pentylheptyl)phenyl)sulfonylamide]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolyl)sulfonylamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pyrrolidin-2,5-dionyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pyrrolidin-2,5-dionyl)phenyl]titanium, -(3,4-dimethyl-3-pyrrolidine-2,5-dionyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phthalimido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((2-chloroethoxy)-carbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylthioureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylthioureido)phenyl]titanium titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N,N-diacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethylureido)phenyl]titanium phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(acetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(decanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octadecanoylamino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylhexanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-methylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethyl-2-methylheptanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(cyclohexylcarbonylamino)phenyl]titanium, bis(cyclo pentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-chloropropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylpropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chloromethyl-2-methyl-3-chloropropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-xylylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-ethylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4,6-mesitylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(benzoylamino) phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylpivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolani-2-ylmethyl)benzoylamino)phenyl]titanium, bi Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolani-2-ylmethyl)-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-toluylmethyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-toluylmethyl)-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzoylamino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,4-dimethylpentyl)-2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,4-dimethylpentyl)-2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4-dimethylpentyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2 ,2-dimethyl-3-ethoxypropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-allyloxypropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-allylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-cyclohexylmethyl-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( N-hexyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)pivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2 ,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-(4-toluyl)amino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-ethyl-2-methylheptanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-ethyl-2-methylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-2,2-dimethylpentanoyl)amino]phenyl]titanium no)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolani-2-ylmethyl)-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(2-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-difluoro-3-(3,3-dimethyl-2-azetidinoni-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanatophenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-butyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropanoyl)-2,2-dimethyl-3-chloropropanoyl )amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropanoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropanoyl)amino)phenyl]titanium , bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanatophenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-tolylsulfonyl)amino)phenyl]titanium, Fluoro-3-(N-hexyl-(4-tolylsulfonyl)amino)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropanoyl)amino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropanoyl)-2,2-dimethyl-3-chloropropanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropanoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylbutanoyl)amino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-ethylpropionylamino)phenyl]titanium, bis(trimethylsilylpentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-trimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylhexyldimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(1,1,2,-trimethylpropyl)dimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-ethoxymethyl-3-methyl-2-azetidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-allyloxymethyl-3-methyl-2-azetidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-chloromethyl bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2-dimethylpropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(5,5-dimethyl-2-pyrrolidinonyl-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(6,6-diphenyl-2-piperidinoni-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,3-dihydro-1,2-benzothiazolo-3-one(1,1-dioxide)-2-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-chlorobenzoyl)amino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-(2-chlorobenzoyl)amino)phenyl]titanium bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)-4-tolyl-sulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-oxaheptyl)benzene bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoromethylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoroacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadiene)bis[2,6-difluoro-3-(trifluoroacetylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,7-dimethyl-7-methoxyoctyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylbenzoylamino)phenyl]titanium, etc. can also be used.

In addition, among the Group 4 element-containing compounds, examples of organic compounds containing zirconium atoms and compounds containing hafnium atoms include (cyclopentadienyl)trimethylzirconium, (cyclopentadienyl)triphenylzirconium, (cyclopentadienyl)tribenzylzirconium, (cyclopentadienyl)trichlorozirconium, (cyclopentadienyl)trimethoxyzirconium, (cyclopentadienyl)dimethyl(methoxy)zirconium, (cyclopentadienyl)methyldichlorozirconium, (methylcyclopentadienyl)trimethylzirconium, (methylcyclopentadienyl)triphenylzirconium, (methylcyclopentadienyl)tribenzylzirconium, (methylcyclopentadienyl)trichlorozirconium, (methylcyclopentadienyl)dimethyl(methoxy)zirconium, (dimethylcyclopentadienyl)trimethylzirconium, ( (Trimethylcyclopentadienyl)trimethylzirconium, (trimethylsilylcyclopentadienyl)trimethylzirconium, (tetramethylcyclopentadienyl)trimethylzirconium, (pentamethylcyclopentadienyl)trimethylzirconium, (pentamethylcyclopentadienyl)triphenylzirconium, (pentamethylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)trichlorozirconium, (pentamethylcyclopentadienyl)trimethoxyzirconium, (pentamethylcyclopentadienyl)dimethyl(methoxy)zirconium, (cyclopentadienyl)triethylzirconium, (cyclopentadienyl)tripropylzirconium, (cyclopentadienyl)trineopentylzirconium, (cyclopentadienyl)tri(diphenylmethyl)zirconium, (cyclopentadienyl)dimethylhis zirconium triethoxy, (cyclopentadienyl)triisopropoxyzirconium, (cyclopentadienyl)triphenoxyzirconium, (cyclopentadienyl)dimethylisopropoxyzirconium, (cyclopentadienyl)diphenylisopropoxyzirconium, (cyclopentadienyl)dimethoxychlorozirconium, (cyclopentadienyl)methoxydichlorozirconium, (cyclopentadienyl)diphenoxychlorozirconium, (cyclopentadienyl)phenoxydichlorozirconium, (cyclopentadienyl)tri(phenyldimethylsilyl)zirconium, (n-butylcyclopentadienyl)dimethyl n-butoxyzirconium, (benzylcyclopentadienyl)di-m-tolylmethylzirconium, (trifluoromethylcyclopentadienyl)tribenzylzirconium, (diphenylsilyl) (cyclopentadienyl) dinorbornyl methyl zirconium, (tetraethylcyclopentadienyl) tribenzyl zirconium, (pentatrimethylsilylcyclopentadienyl) tribenzyl zirconium, (pentamethylcyclopentadienyl) trimeopentyl zirconium, (pentamethylcyclopentadienyl) methyl dichloro zirconium, (pentamethylcyclopentadienyl) triethoxy zirconium, (pentamethylcyclopentadienyl) triphenoxy zirconium, (pentamethylcyclopentadienyl) methoxy dichloro zirconium, (pentamethylcyclopentadienyl) diphenoxy chloro zirconium, (pentamethylcyclopentadienyl) phenoxy dichloro zirconium, (indenyl) trimethyl zirconium, (indenyl) tribenzyl zirconium, (indenyl) trichloro zirconium, (indenyl) trimethoxy zirconium,

(indenyl)triethoxyzirconium, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)diethylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)dimethoxyzirconium, bis(cyclopentadienyl)dichlorozirconium, bis(cyclopentadienyl)dihydridozirconium, bis(cyclopentadienyl) ) chlorohydrido zirconium, bis(methylcyclopentadienyl)dimethyl zirconium, bis(methylcyclopentadienyl)dibenzyl zirconium, bis(methylcyclopentadienyl)dichloro zirconium, bis(pentamethylcyclopentadienyl)dimethyl zirconium, bis(pentamethylcyclopentadienyl)dibenzyl zirconium, bis(pentamethylcyclopentadienyl)dichloro zirconium, bis(pentamethylcyclopentadienyl ) chloromethylzirconium, bis(pentamethylcyclopentadienyl)hydridomethylzirconium, (cyclopentadienyl)(pentamethylcyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)dime-m-tolylzirconium, bis(cyclopentadienyl)dime-p-tolylzirconium, bis(cyclopentadienyl)bis(diphenylmethyl)zirconium, bis(cyclopenta bis(cyclopentadienyl)dibromo zirconium, bis(cyclopentadienyl)methyl chlorozirconium, bis(cyclopentadienyl)ethyl chlorozirconium, bis(cyclopentadienyl)cyclohexyl chlorozirconium, bis(cyclopentadienyl)phenyl chlorozirconium, bis(cyclopentadienyl)benzyl chlorozirconium, bis(cyclopentadienyl)hydridomethyl zirconium, bis(cyclopentadienyl)methoxy chlorozirconium,

Bis(cyclopentadienyl)ethoxychlorozirconium, bis(cyclopentadienyl)(trimethylsilyl)methylzirconium, bis(cyclopentadienyl)bis(trimethylsilyl)zirconium, bis(cyclopentadienyl)(triphenylsilyl)methylzirconium, bis(cyclopentadienyl)(tris(dimethylsilyl)silyl)methylzirconium, bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium, bis(methylcyclopentadienyl)diphenylzirconium, bis(ethylcyclopenta bis(cyclopentadienyl)dimethylzirconium, bis(ethylcyclopentadienyl)dichlorozirconium, bis(propylcyclopentadienyl)dimethylzirconium, bis(propylcyclopentadienyl)dichlorozirconium, bis(n-butylcyclopentadienyl)dichlorozirconium, bis(t-butylcyclopentadienyl)bis(trimethylsilyl)zirconium, bis(hexylcyclopentadienyl)dichlorozirconium, bis(cyclohexylcyclopentadienyl)dimethylzirconium, bis(dimethylcyclopentadienyl)dimethylzirconium , bis(dimethylcyclopentadienyl)dichlorozirconium, bis(dimethylcyclopentadienyl)ethoxychlorozirconium, bis(ethylmethylcyclopentadienyl)dichlorozirconium, bis(propylmethylcyclopentadienyl)dichlorozirconium, bis(butylmethylcyclopentadienyl)dichlorozirconium, bis(trimethylcyclopentadienyl)dichlorozirconium, bis(tetramethylcyclopentadienyl)dichlorozirconium, bis(cyclohexylmethylcyclopentadienyl)dibenzylzirconium, bis( Bis(trimethylsilylcyclopentadienyl)dimethylzirconium, bis(trimethylsilylcyclopentadienyl)dichlorozirconium, bis(trimethylgermylcyclopentadienyl)dimethylzirconium, bis(trimethylgermylcyclopentadienyl)diphenylzirconium, bis(trimethylstannylcyclopentadienyl)dimethylzirconium, bis(trimethylstannylcyclopentadienyl)dibenzylzirconium, bis(trifluoromethylcyclopentadienyl)dimethylzirconium, bis(trifluoromethylcyclopentadienyl)dimethylzirconium, bis(indenyl)dinorbornylzirconium, bis(indenyl)dibenzylzirconium, bis(indenyl)dichlorozirconium, bis(indenyl)dibromodi- zirconium, bis(tetrahydroindenyl)dichlorozirconium, bis(fluorenyl)dichlorozirconium, (propylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)dibenzylzirconium, (pentatrimethylsilylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, (trimethylsilylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, trifluoromethylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, ethylene bis(indenyl)dimethylzirconium, ethylene bis(indenyl)dichlorozirconium, ethylene bis(tetrahydroindenyl)dimethylzirconium, ethylene bis(tetrahydroindenyl)dichlorozirconium, dimethylsilylenebis(cyclopentadienyl)dimethylzirconium, dimethylsilylenebis(cyclopentadienyl)dichlorozirconium, isopropylidene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium, isopropylidene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium, isopropylidene(cyclopentadienyl)(9-fluorenyl)dichlorozirconium, [phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl)dimethylzirconium, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium, ethylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, cyclohexylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, cyclopentylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, cyclobutylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, Dene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, dimethylsilylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dimethylzirconium, dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium, dimethylsilylenebis(indenyl)dichlorozirconium, methylenebis(cyclopentadienyl)dimethylzirconium, methylenebis(cyclopentadienyl)di(trimethylsilyl)zirconium,

Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethyl zirconium, methylene (cyclopentadienyl) (fluorenyl) dimethyl zirconium, ethylene bis (cyclopentadienyl) dimethyl zirconium, ethylene bis (cyclopentadienyl) dibenzyl zirconium, ethylene bis (cyclopentadienyl) dihydrido zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methylchloro zirconium, ethylene bis (tetrahydroindenyl) dibenzyl zirconium, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) dichloro zirconium, isopropylidene (cyclopentadienyl) (octahydrofluorenyl) dihydrido zirconium, dimethylsilylene bis (cyclopentadienyl) dineopentyl zirconium, dimethylsilylene bis (cyclopentadienyl) dihydrido zirconium hafnium, dimethylsilylene bis(methylcyclopentadienyl) dichlorozirconium, dimethylsilylene bis(dimethylcyclopentadienyl) dichlorozirconium, dimethylsilylene bis(tetrahydroindenyl) dichlorozirconium, dimethylsilylene(cyclopentadienyl)(fluorenyl) dichlorozirconium, dimethylsilylene(cyclopentadienyl)(fluorenyl) dihydrido zirconium, dimethylsilylene(methylcyclopentadienyl)(fluorenyl) dihydrido zirconium, dimethylsilylene bis(3-trimethylsilylcyclopentadienyl) dihydrido zirconium, dimethylsilylene bis(indenyl) dimethylzirconium, diphenylsilylene bis(indenyl) dichlorozirconium, phenylmethylsilylene bis(indenyl) dichlorozirconium, and compounds in which the zirconium atoms in these compounds are replaced with hafnium atoms can also be used.

Other examples of the metal element-containing compound include compounds containing iron atoms, palladium atoms, nickel atoms, and the like.
The compound containing an iron atom is preferably a complex compound containing an iron atom, and more preferably a metallocene compound such as ferrocene.
The compound containing a palladium atom or a nickel atom is more preferably a complex compound containing a palladium atom or a nickel atom.
The compound containing an iron atom, a palladium atom, a nickel atom, or the like may or may not have radical polymerization initiation ability, but preferably has radical polymerization initiation ability.

The content of the metal element-containing compound is preferably 0.1 to 30% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
The metal element-containing compound may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

In addition, in the composition of the present invention, the mass ratio of the content of the metal element-containing compound to the content of the onium salt or other thermal base generator described below, metal element-containing compound: onium salt or other thermal base generator, is preferably 99:1 to 1:99, more preferably 90:10 to 10:90, and even more preferably 40:60 to 20:80. By setting the ratio in such a range, it is possible to achieve a higher ring closure rate of the precursor at low temperatures and a higher glass transition temperature.

<Polymerizable Compound>
[Radically polymerizable compound]
The composition of the present invention preferably contains a polymerizable compound.
As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. As the radical polymerizable group, a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, or a (meth)acryloyl group can be mentioned. As the radical polymerizable group, a (meth)acryloyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferable.

The number of radically polymerizable groups in the radically polymerizable compound may be one or two or more, but it is preferable that the radically polymerizable compound has two or more radically polymerizable groups, and more preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radical polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, even more preferably 900 or less, and particularly preferably 600 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

From the viewpoint of developability, the composition of the present invention preferably contains at least one type of radically polymerizable compound having two or more radically polymerizable groups and is more preferably at least one type of radically polymerizable compound having three or more functional groups. It may also be a mixture of a radically polymerizable compound having two or more functional groups and a radically polymerizable compound having three or more functional groups. For example, the number of functional groups of a polymerizable monomer having two or more functional groups means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

In addition, the radical polymerizable compound is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of such compounds include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, and many other compounds. Examples of suitable compounds include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the compound, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-A-52-030490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Examples of suitable polyfunctional (meth)acrylates include those obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

Other preferred radical polymerizable compounds that can be used include compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A-2010-160418, JP-A-2010-129825, Japanese Patent No. 4,364,216, etc., and cardo resins.

Other examples include the specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and the vinylphosphonic acid compounds described in JP-A-02-025493. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015/199219 A can also be preferably used, the contents of which are incorporated herein by reference.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) along with specific examples thereof, can also be used as radical polymerizable compounds.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as other radical polymerizable compounds, the contents of which are incorporated herein by reference.

As radical polymerizable compounds, dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl groups of these compounds are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligomer types of these compounds can also be used.

Commercially available radical polymerizable compounds include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Corporation, SR-209, 231, and 239, difunctional methacrylates having four ethyleneoxy chains manufactured by Sartomer Corporation, DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three isobutyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., and urethane Examples include N-oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

As radical polymerizable compounds, urethane acrylates as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Furthermore, as radical polymerizable compounds, compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxy group or a phosphate group. The radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical polymerizable compound in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred is a radical polymerizable compound in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radically polymerizable compound is within the above range, the compound has excellent handling properties during production and excellent developability. The compound also has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of suppressing warpage associated with controlling the elastic modulus of the organic film, the composition of the present invention can preferably use a monofunctional radically polymerizable compound as the radically polymerizable compound. As the monofunctional radically polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100°C or higher under normal pressure is also preferred in order to suppress volatilization before exposure.

[Polymerizable compounds other than the above-mentioned radically polymerizable compounds]
The composition of the present invention may further contain a polymerizable compound other than the above-mentioned radical polymerizable compound. Examples of the polymerizable compound other than the above-mentioned radical polymerizable compound include a compound having a hydroxymethyl group (methylol group), an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

-Compounds 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), (AM4) or (AM5) is preferable.

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a valence of t and containing 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(In the formula, u is an integer of 3 to 8, R ⁵⁰⁴ is an organic group having u valence and 1 to 200 carbon atoms, R ⁵⁰⁵ is a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ is an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC Examples include MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, and 2,6-diacetoxymethyl-p-cresol.

Specific examples of the compound represented by 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 (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

-Epoxy compound (compound having an epoxy group)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200° C. or less, and does not undergo a dehydration reaction due to crosslinking, so film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the composition at low temperatures and suppressing warping.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether, and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specific examples include Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-200, Epicron (registered trademark) EXA-151, Epicron (registered trademark) EXA-20 ... Examples of epoxy resins include Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron (registered trademark) EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (all trade names, manufactured by ADEKA Corporation). Among these, epoxy resins containing polyethylene oxide groups are preferred in terms of their excellent warpage suppression and heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Likaresin (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

--Oxetane compound (compound having an oxetanyl group)--
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

-Benzoxazine compound (compound having a benzoxazolyl group)-
Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that no degassing occurs during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of the polymerizable compound is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

One type of polymerizable compound may be used alone, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.

<Solvent>
The composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) Suitable examples include 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

Suitable examples of ethers include 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, and propylene glycol monopropyl ether acetate.

Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

A suitable example of a sulfoxide is dimethyl sulfoxide.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

From the viewpoint of improving the properties of the coating surface, it is also preferable to mix two or more types of solvents.

In the present invention, one solvent selected from 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, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more of them, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the composition of the present invention of 5 to 80% by mass, more preferably an amount that results in a total solids concentration of 5 to 75% by mass, even more preferably an amount that results in a total solids concentration of 10 to 70% by mass, and even more preferably an amount that results in a total solids concentration of 40 to 70% by mass. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

The composition may contain only one type of solvent, or two or more types. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.

<Thermal Polymerization Initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be advanced in the heating step described below, so that the solvent resistance can be further improved.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% based on the total solid content of the composition of the present invention, more preferably 0.1 to 20 mass%, and even more preferably 5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

<Thermal Acid Generator>
The compositions of the present invention may also include a thermal acid generator.
The thermal acid generator generates an acid upon heating, and has the effect of promoting the 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.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select as the thermal acid generator a material that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (cure: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of JP2013-072935A.

Among these, from the viewpoint of having little residue in the organic film and being less likely to deteriorate the physical properties of the organic film, those which generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferable, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl (4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium methanesulfonate, and (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate. nium, trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonate benzyl (4-hydroxyphenyl)methylsulfonium, trifluoromethanesulfonate benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, trifluoromethanesulfonate (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as thermal acid generators.

The compounds described in paragraph 0059 of JP2013-167742A are also preferred as thermal acid generators.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Onium salt>
The composition of the present invention preferably contains an onium salt.
In particular, when the composition contains a polyimide precursor as the other resin, it is preferable that the composition contains an onium salt.
The type of onium salt is not particularly limited, but preferred examples include ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond.
That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionic-bonded, but an intermolecular salt is preferable. In addition, in the composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded by an ionic bond or may be dissociated.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

The onium salt used in the present invention may be a thermal base generator.
The thermal base generator refers to a compound that generates a base when heated, and examples thereof include acidic compounds that generate a base when heated to 40° C. or higher.

[Ammonium salt]
In the present invention, an ammonium salt means a salt of an ammonium cation and an anion.

- Ammonium cation -
The ammonium cation is preferably a quaternary ammonium cation.
Moreover, the ammonium cation is preferably a cation represented by the following formula (101).

In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to form a ring.

In formula (101), R ¹ to R ⁴ are each preferably independently a hydrocarbon group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like.
When at least two of R ¹ to R ⁴ are bonded to each other to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2).

In formulae (Y1-1) and (Y1-2), R ¹⁰¹ represents an n-valent organic group, R ¹ has the same meaning as R ¹ in formula (101), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, and n represents an integer of 1 or more.
In formula (Y1-1), R ¹⁰¹ is preferably a group in which n hydrogen atoms have been removed from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure in which these are bonded, and more preferably a group in which n hydrogen atoms have been removed from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene.
In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² each independently preferably represent a phenyl group or a naphthyl group, and more preferably a phenyl group.

- Anion -
The anion in the ammonium salt is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and more preferably a carboxylate anion because it can provide both stability and thermal decomposition of the salt. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, and more preferably an anion of a divalent carboxylic acid. According to this embodiment, the stability, curability, and developability of the composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the composition can be further improved.

The carboxylate anion is preferably represented by the following formula (X1).

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

In this embodiment, the electron-withdrawing group refers to a group having a Hammett's substituent constant σm that is a positive value. Here, σm is explained in detail in Yuho Miyano's Review, Journal of the Society of Organic Synthesis, Vol. 23, No. 8 (1965), pp. 631-642. Note that the electron-withdrawing group in this embodiment is not limited to the substituents described in the above document.
Examples of substituents with a positive σm value include a _CF3 group (σm=0.43), a _CF3C (=O) group (σm=0.63), a HC≡C group (σm=0.21), a _CH2 =CH group (σm=0.06), an Ac group (σm=0.38), a MeOC(=O) group (σm=0.37), a MeC(=O)CH=CH group (σm=0.21), a PhC(=O) group (σm=0.34), and a _H2NC (=O) _CH2 group (σm=0.06). Note that Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

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 carboxy group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is preferably represented by the following formula (XA).

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

Specific examples of carboxylate anions include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion.

From the viewpoints of cyclization of the specific resin being easily carried out at low temperatures and of easily improving the storage stability of the composition, the onium salt in the present invention preferably contains an ammonium cation as a cation, and the onium salt preferably contains an anion having a conjugate acid with a pKa (pKaH) of 2.5 or less, and more preferably an anion with a pKaH of 1.8 or less, as an anion.
The lower limit of the pKa is not particularly limited, but from the viewpoint of making the generated base less likely to be neutralized and improving the cyclization efficiency of a specific resin or the like, it is preferably −3 or more, and more preferably −2 or more.
As the pKa, values described in Determination of Organic Structures by Physical Methods (authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; edited by: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, values calculated from the structural formula using ACD/pKa software (manufactured by ACD/Labs) will be used.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[Iminium salts]
In the present invention, the iminium salt refers to a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Iminium cation-
The iminium cation is preferably a pyridinium cation.
As the iminium cation, a cation represented by the following formula (102) is also preferred.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and at least two of R ⁵ to R ⁷ may be bonded to form a ring.
In formula (102), R ⁵ and R ⁶ have the same meanings as R ¹ to R ⁴ in formula (101) above, and preferred embodiments are also the same.
In formula (102), ^R7 is preferably bonded to at least one of ^R5 and ^R6 to form a ring. The ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom. The ring is preferably a pyridine ring.

The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).

In formulae (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same meaning as R ⁵ in formula (102), R ⁷ has the same meaning as R ⁷ in formula (102), n represents an integer of 1 or more, and m represents an integer of 0 or more.
In formula (Y1-3), R ¹⁰¹ is preferably a group in which n hydrogen atoms have been removed from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure in which these are bonded, and more preferably a group in which n hydrogen atoms have been removed from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene.
In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In formula (Y1-5), m is preferably an integer of 0 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of iminium salts include the following compounds, but the present invention is not limited to these.

[Sulfonium salts]
In the present invention, the sulfonium salt refers to a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
Moreover, the sulfonium cation is preferably a cation represented by the following formula (103).

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
Each of R ⁸ to R ¹⁰ independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, it is preferable that the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferable that they are the same group.

[Iodonium salts]
In the present invention, the iodonium salt refers to a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Iodonium cation-
The iodonium cation is preferably a diaryliodonium cation.
Moreover, the iodonium cation is preferably a cation represented by the following formula (104).

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, it is preferable that the substituent has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.

[Phosphonium Salts]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, such as a tetraalkylphosphonium cation or a triarylmonoalkylphosphonium cation.
Moreover, the phosphonium cation is preferably a cation represented by the following formula (105).

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
Each of R ¹³ to R ¹⁶ independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among these, it is preferable that the substituent has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.

When the composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass% based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5 mass% or more, even more preferably 0.85 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, even more preferably 20 mass% or less, and still more preferably 10 mass% or less, and may be 5 mass% or less, or may be 4 mass% or less.
The onium salt may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

<Thermal Base Generator>
The compositions of the present invention may include a thermal base generator.
In particular, when the composition contains a polyimide precursor as the other resin, the composition preferably contains a thermal base generator.
The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt.
Other examples of the thermal base generator include nonionic thermal base generators.
Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not simultaneously hydrogen atoms. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when it forms an amide group together with the nitrogen atom.

In formula (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. In particular, ^Rb1 and ^Rb2 are preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

Rb ³ is an alkyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an alkenyl group (having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), an arylalkyl group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), an arylalkenyl group (having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), an alkoxyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryloxy group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyloxy group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. ^Rb3 may further have a substituent within the range in which the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent within the range in which the effects of the present invention are exhibited. Among these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are each a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, specific examples of the compounds which are thermal base generators or specific examples of other thermal base generators include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or more types of thermal base generators can be used. When two or more types are used, it is preferable that the total amount is in the above range.

<Migration Inhibitor>
The composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the composition layer.

The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferably used.

Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219.

Specific examples of migration inhibitors include the following compounds:

When the composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the composition.

The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total amount is within the above range.

<Polymerization inhibitor>
The composition of the present invention preferably contains a polymerization inhibitor.

Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 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, and N-phenylnaphthylamine. , ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. are preferably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 A can also be used.

The following compounds can also be used (Me is a methyl group):

When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass %, based on the total solid content of the composition of the present invention.

The polymerization inhibitor may be of only one type, or of two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total amount is within the above range.

<Metal adhesion improver>
The composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents.

Examples of silane coupling agents include the compounds described in paragraph 0167 of WO 2015/199219, the compounds described in paragraphs 0062-0073 of JP 2014-191002 A, the compounds described in paragraphs 0063-0071 of WO 2011/080992 A, the compounds described in paragraphs 0060-0061 of JP 2014-191252 A, the compounds described in paragraphs 0045-0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of WO 2014/097594 A. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050-0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

In addition, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used as metal adhesion improvers.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the organic film and the metal layer after the curing process is good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the organic film after the curing process are good. 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, it is preferable that the total amount is within the above range.

<Other additives>
The composition of the present invention may contain various additives as necessary, for example, sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. When these additives are contained, the total amount is preferably 3% by mass or less of the solid content of the composition.

[Sensitizer]
The composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose, generating a radical, an acid, or a base.
The sensitizer includes sensitizers such as N-phenyldiethanolamine.
As the sensitizer, a sensitizing dye may be used.
For details about the sensitizing dye, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, the contents of which are incorporated herein by reference.

When the composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the composition of the present invention. The sensitizer may be used alone or in combination of two or more kinds.

[Chain transfer agent]
The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. As chain transfer agents, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These can donate hydrogen to a low activity radical to generate a radical, or can be oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

The chain transfer agent may also be the compound described in paragraphs 0152 to 0153 of WO 2015/199219.

When the composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the composition of the present invention. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, it is preferable that the total amount is in the above range.

[Surfactant]
In order to further improve the coating property, various types of surfactants may be added to the composition of the present invention. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repeats of each repeating unit.

In addition, the surfactant may be the compound described in paragraphs 0159 to 0165 of WO 2015/199219.

When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be one type or two or more types. When two or more types of surfactants are used, the total amount is preferably within the above range.

[Higher fatty acid derivatives]
In order to prevent polymerization inhibition caused by oxygen, the composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the composition during drying after application.

The higher fatty acid derivative may also be the compound described in paragraph 0155 of WO 2015/199219.

When the composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total amount is preferably within the above range.

<Restrictions on other substances>
The water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface.

From the viewpoint of insulation, the metal content of the composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are contained, it is preferable that the total amount of these metals is within the above range.

Methods for reducing metal impurities unintentionally contained in the composition of the present invention include selecting raw materials with low metal content as the raw materials constituting the composition of the present invention, filtering the raw materials constituting the composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Considering the use of the composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more 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 even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.

Conventionally known containers can be used as containers for the composition of the present invention. In addition, it is also preferable to use, as the container, a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin, in order to prevent impurities from being mixed into the raw materials or the composition. Examples of such containers include the containers described in JP 2015-123351 A.

<Preparation of Composition>
The composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be any method known in the art.

In addition, it is preferable to perform filtration using a filter in order to remove foreign matter such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. In addition, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be performed. In addition, filtration may be performed under pressure. When filtering under pressure, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.

<Applications of organic films>
The organic film of the present invention is preferably used as an interlayer insulating film for a rewiring layer.
In addition, the film may also be used as an insulating film or a stress buffer film in a semiconductor device.

(Composition)
The composition of the present invention is a composition used to form the organic film of the present invention.
The components contained in the composition of the present invention are the same as those in the composition described above for the organic film, and preferred embodiments are also the same.
The composition of the present invention is preferably a curable composition that is cured by exposure to light, heating, or the like.

(Organic film, laminate, semiconductor device, and manufacturing method thereof)
Next, an organic film, a laminate, a semiconductor device, and methods for manufacturing them will be described.

The organic film of the present invention is preferably a cured product of a coating film of the composition. The thickness of the organic film of the present invention can be, for example, 0.5 μm or more, or 1 μm or more. The upper limit can be 100 μm or less, or 30 μm or less.

The organic film of the present invention may be laminated in two or more layers, or even three to seven layers, to form a laminate. The laminate of the present invention is preferably a laminate having two or more organic films and a metal layer between the organic films. In addition, the laminate of the present invention is preferably an embodiment that includes two or more organic films and includes a metal layer between any of the organic films. For example, a laminate including at least a layer structure in which three layers, a first organic film, a metal layer, and a second organic film, are laminated in this order, is preferred. Both the first organic film and the second organic film are organic films of the present invention, and for example, both the first organic film and the second organic film are films formed by curing the composition of the present invention. The composition of the present invention used to form the first organic film and the composition of the present invention used to form the second organic film may be compositions having the same composition or different compositions, but from the viewpoint of manufacturing suitability, it is preferable that they have the same composition. Such a metal layer is preferably used as metal wiring such as a rewiring layer.

The organic film of the present invention can be applied to insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), and the formation of patterns by etching of insulating films for mounting applications such as those mentioned above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd. "High-performance and Applied Technology of Polyimide" April 2008, edited by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association "Latest Polyimide Basics and Applications" NTS, August 2010.

The organic films of the present invention can also be used in the manufacture of printing plates, such as offset printing plates or screen printing plates, for etching molded parts, and for the manufacture of protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing an organic film of the present invention (hereinafter also simply referred to as the "production method of the present invention") preferably includes a film formation step of applying a composition (the composition of the present invention) to a substrate to form a film.
Furthermore, the method for producing an organic film of the present invention preferably includes the film forming step, and further includes an exposure step of exposing the film to light and a development step of developing the film (subjecting the film to a development treatment).
Moreover, the method for producing an organic film of the present invention more preferably includes the above-mentioned film forming step (and, if necessary, the above-mentioned developing step) and further includes a heating step of heating the above-mentioned film at 50 to 450°C.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film-forming step of applying a composition to a substrate to form a film (composition layer), (b) an exposure step of exposing the film after the film-forming step, (c) a development step of developing the exposed film, and (d) a heating step of heating the developed film at 50 to 450° C. By heating in the heating step, the composition layer after development can be further cured. In this heating step, for example, the thermal base generator described above is decomposed, and sufficient curability is obtained.

The method for manufacturing a laminate according to a preferred embodiment of the present invention includes the method for manufacturing an organic film according to the present invention. In the method for manufacturing a laminate according to the present embodiment, after forming an organic film according to the method for manufacturing an organic film, step (a) or steps (a) to (c) or steps (a) to (d) are performed again. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By stacking the organic films in this way, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the part where the organic film is provided, between the organic films, or on both. In addition, in the manufacture of a laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, a laminate of organic films can be obtained by performing at least (a), preferably steps (a) to (c) or (a) to (d) multiple times.

<Film formation process (layer formation process)>
A production method according to a preferred embodiment of the present invention includes a film-forming step (layer-forming step) of applying a composition to a substrate to form a film (layer).

The type of substrate can be appropriately determined depending on the application, but is not particularly limited to substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and electrode plates for plasma display panels (PDPs). In the present invention, substrates for semiconductor production are particularly preferred, and silicon substrates are more preferred.
As the base material, for example, a plate-shaped base material (substrate) is used.

When a composition layer is formed on the surface of a resin layer such as a composition layer or on the surface of a metal layer, the resin layer or metal layer serves as the substrate.

The preferred method for applying the composition to the substrate is coating.

Specifically, examples of the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an inkjet method. From the viewpoint of uniformity of the thickness of the composition layer, more preferred are a spin coating method, a slit coating method, a spray coating method, and an inkjet method. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer of a desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferred, and if the substrate is a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, etc. are preferred. In the case of the spin coating method, for example, it can be applied for about 10 seconds to 1 minute at a rotation speed of 500 to 2,000 rpm (revolutions per minute).
Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
Regarding the transfer method, the methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after forming the film (composition layer) and after the film forming step (layer forming step). The drying temperature is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (composition layer) to light. The amount of exposure is not particularly limited as long as the composition can be cured, but for example, it is preferable to irradiate with 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated as exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

In terms of the light source, the exposure wavelength may be, in terms of the relationship with the light source, (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, etc. For the composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. This allows for particularly high exposure sensitivity to be obtained.

<Developing process>
The manufacturing method of the present invention may include a development step in which a development process is performed on the exposed film (composition layer). By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as it can form a desired pattern, and for example, a development method such as paddle, spray, immersion, or ultrasonic can be used.

The development is carried out using a developer. The developer can be any developer that removes the unexposed portion of the composition layer if the composition is a negative composition, or any developer that removes the exposed portion of the composition layer if the composition is a positive composition, without any particular limitation.
In the present invention, the case where an alkaline developer is used as the developer is referred to as alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is referred to as solvent development.

In alkaline development, the developer preferably has an organic solvent content of 10 mass % or less, more preferably 5 mass % or less, and even more preferably 1 mass % or less, based on the total mass of the developer, and particularly preferably does not contain any organic solvent.
The developer in the alkaline development is preferably an aqueous solution having a pH of 9 to 14.
Examples of the alkaline compound contained in the developer in the alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia, and amines. Examples of the amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Among these, alkali compounds not containing metal are preferred, and ammonium compounds are more preferred.
Only one type of alkaline compound may be used, or two or more types may be used. When two or more types of alkaline compounds are used, the total amount is preferably within the above range.

In solvent development, it is more preferable that the developer contains 90% or more of an organic solvent. In the present invention, it is preferable that the developer contains an organic solvent with a ClogP value of -1 to 5, and more preferably an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated by inputting the structural formula in ChemBioDraw.

The organic solvent may be, for example, an ester, such as ethyl acetate, n-butyl 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 alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., as well as ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., as well as aromatic hydrocarbons such as toluene, xylene, anisole, limonene, etc., and as sulfoxides such as dimethyl sulfoxide are preferred.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, with cyclopentanone being more preferred.

The developer preferably contains 50% by weight or more of organic solvent, more preferably 70% by weight or more of organic solvent, and even more preferably 90% by weight or more of organic solvent. The developer may also contain 100% by weight of organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but can usually be 20 to 40°C.

After the treatment with the developer, a rinsing step may be further carried out.
In the case of solvent development, rinsing is preferably carried out using an organic solvent different from the developer.
In the case of alkaline development, rinsing is preferably carried out using pure water.
The rinsing time is preferably from 5 seconds to 1 minute.

<Heating process>
The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
In this step, the curing reaction of unreacted polymerizable compounds other than the specific resin contained in the composition of the present invention, the curing reaction of unreacted polymerizable groups in the specific resin, etc. can proceed.
Furthermore, in the case where the specific resin is a polyimide precursor and the composition contains a thermal base generator, in the heating step, for example, the thermal base generator is decomposed to generate a base, and a cyclization reaction of the polyimide precursor proceeds.
The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, even more preferably 140° C. or higher, particularly preferably 150° C. or higher, even more preferably 160° C. or higher, and most preferably 170° C. or higher. The upper limit is preferably 450° C. or lower, more preferably 350° C. or lower, even more preferably 250° C. or lower, and particularly preferably 220° C. or lower.

The heating is preferably performed at a temperature rise rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature rise rate at 1°C/min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the temperature rise rate at 12°C/min or less, it is possible to alleviate the residual stress in the organic film.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the composition is applied to a substrate and then dried, it is the temperature of the film (layer) after this drying, and it is preferable to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the composition.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of adhesion between the organic film layers, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is unclear, but it is thought that by heating at this temperature, crosslinking reactions between polymerizable groups in the resin between the layers proceed.

Heating may be performed in stages. For example, a pretreatment step may be performed in which the temperature is increased from 25°C to 180°C at 3°C/min, held at 180°C for 60 minutes, increased from 180°C to 200°C at 2°C/min, and held at 200°C for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in U.S. Patent No. 9,159,547. Such a pretreatment step can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, pretreatment step 1 may be performed in the range of 100 to 150°C, and then pretreatment step 2 may be performed in the range of 150 to 200°C.

Furthermore, after heating, the material may be cooled, in which case the cooling rate is preferably 1 to 5°C/min.

The heating process is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal Layer Forming Process>
The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (composition layer) after development treatment.

The metal layer is not particularly limited and existing metal species can be used, examples of which include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten, with copper and aluminum being more preferred, and copper being even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods can be considered. More specifically, examples include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.

The thickness of the metal layer is preferably 0.1 to 50 μm at its thickest part, and more preferably 1 to 10 μm.

<Lamination process>
The manufacturing method of the present invention preferably further includes a lamination step.

The lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process, which are carried out again on the surface of the organic film (resin layer) or metal layer in this order. However, it is also possible to repeat only the film formation process (a). In addition, the heating process (d) may be carried out all at once at the end or in the middle of the lamination. In other words, it is also possible to repeat the processes (a) to (c) a predetermined number of times, and then carry out heating (d) to cure the laminated composition layers all at once. In addition, after the development process (c), it is also possible to include the metal layer formation process (e), and at this time, heating (d) may be carried out each time, or heating (d) may be carried out all at once after lamination a predetermined number of times. It goes without saying that the lamination process may further include the above-mentioned drying process, heating process, etc. as appropriate.

If a further lamination step is performed after the lamination step, a surface activation treatment step may be performed after the heating step, the exposure step, or the metal layer formation step. An example of the surface activation treatment is a plasma treatment.

The lamination process is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

For example, a structure with 3 to 7 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure with 3 to 5 resin layers is even more preferred.

In the present invention, it is particularly preferable to form an organic film (resin layer) of the above composition so as to cover the metal layer after providing the metal layer. Specifically, the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step, or the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, and (e) metal layer formation step, with (d) heating step being provided at the end or in the middle. The composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the composition layer (resin layer) and the metal layer formation step.

The present invention also discloses a semiconductor device including the organic film or laminate of the present invention. Specific examples of semiconductor devices using the composition of the present invention to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP2016-027357A, the contents of which are incorporated herein by reference.

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following, "parts" and "%" are based on mass unless otherwise specified.

(Synthesis of polyimide precursor PA-1)
20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a stirrer, a condenser and a flat-bottom joint equipped with an internal thermometer. 10.1 g (77 mmol) of 2-hydroxyethyl methacrylate, 12.6 g (39 mmol) of Blenmar AP-400 (NOF Corp.), 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively and stirred at a temperature of 60° C. for 18 hours. The mixture was then cooled to −20° C., after which 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature (23° C.) and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added, obtaining a clear solution. Then, 11.7 g (58.7 mmol) of 4,4'-diaminodiphenyl ether as diamine dissolved in 100 mL of NMP was added dropwise to the obtained clear solution over 1 hour. Viscosity increased during the addition of the diamine. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C under reduced pressure for 1 day. The molecular weight of this polyimide precursor resin PA-1 was Mw=25,100 and Mn=13,200.
The structure of PA-1 is presumed to be a structure represented by the following formula (PA-1): In formula (PA-1), * represents the bonding site with the oxygen atom to which R is bonded.
In the above (PA-1), the description of C ₃ H ₆ randomly contains 1-methylethylene groups (formula (P1) below) and 2-methylethylene groups (formula (P2) below). In formulas (P1) and (P2), * ¹ bonds to the structure on the acryloxy group side in R in formula (PA-1), and * ² bonds to the structure on the * side in R in formula (PA-1).

<Examples and Comparative Examples>
In each example, each composition was obtained by mixing the components shown in Table 1. In each comparative example, each comparative composition was obtained by mixing the components shown in Table 1. The obtained compositions and comparative compositions were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In Table 1, the numerical values in each column indicate the content (mass %) of each component in the composition.
The value in the "Total" column indicates the total content (mass %) of each component in the composition.
In addition, in Table 1, the notation "-" indicates that the corresponding component is not contained.

Details of each component listed in Table 1 are as follows:

〔solvent〕
NMP: N-methylpyrrolidone GBL: γ-butyrolactone DMSO: dimethylsulfoxide EL: ethyl lactate

[Initiator]
OXE01: Irgacure OXE01 (manufactured by BASF)
・ 784EG: Irgacure 784 EG (manufactured by BASF)

〔resin〕
PA-1: Polyimide precursor resin PA-1 synthesized above

[Polymerizable compound]
SR 209: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer Corporation)
DPHA: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

〔Silane coupling agent〕
S-1 to S-2: Compounds having the following structures

[Polymerization inhibitor]
F-1: 1,4-benzoquinone F-2: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd., compound having the following structure)

[Onium salt or thermal base generator]
T-1: Compound having the following structure

[Migration Inhibitor]
H-1: 1H-tetrazole H-2: Compound having the following structure

<Evaluation>
[Small angle neutron scattering (SANS) measurement]
Each of the compositions prepared in the Examples and Comparative Examples or the comparative compositions was applied onto a silicon wafer by spin coating to form a resin layer.
The silicon wafer on which the resin layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. The obtained composition layer was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 . After the exposure, the temperature was increased at a rate of 10°C/min under a nitrogen atmosphere, and after reaching 180°C, the layer was heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the organic film was peeled off from the silicon wafer.
The organic film obtained by the above method and having a thickness of about 15 μm was cut into a circle having a diameter of 18 mm, and the cut pieces were stacked to a thickness of 100 to 200 μm to prepare a measurement sample. After measuring the mass and film thickness of the measurement sample, the sample was filled into a sample holder dedicated to SANS measurement of J-PARC MLF iMATERIA and sealed.

Using the sample holder filled with the above-mentioned measurement sample, small angle neutron scattering measurements were performed using J-PARC MLF iMATERIA (BL20). Specifically, the above-mentioned sample holder was placed in a 40-series automatic sample changer dedicated to SANS measurements, and automatic measurements were performed. The measurement conditions were as follows:
In addition, in order to calculate the relative intensity value, a measurement was performed using an empty sample holder that was not filled with a measurement sample under the same measurement conditions as the above measurement.

-Measurement condition-
MLF neutron beam output: 500 kW
Measurement q value range: 0.007 to 5 Å ⁻¹ (the small angle detector bank (0.007 to 0.5 Å ⁻¹ ) and the low angle detector bank (0.5 to 5 Å ⁻¹ ) of the above J-PARC MLF iMATERIA (BL20) were used.)
Measurement temperature: room temperature (23°C)
Accumulation time: 12-15 min/sample

From the measurement results, the values of I/A and I/B were calculated for each Example and Comparative Example, and listed in the "I/A" or "I/B" columns in Table 1, respectively.

[Evaluation of Solvent Resistance]
Each of the compositions prepared in the Examples and Comparative Examples or the Comparative Compositions was applied to a silicon wafer having a diameter of 4 inches by spin coating to form a resin layer.
The silicon wafer on which the resin layer was formed was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. The obtained composition layer was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm ^2. After the exposure, the temperature was increased at a rate of 10° C./min under a nitrogen atmosphere, and after reaching 180° C., the temperature was heated for 3 hours to obtain a silicon wafer on which an organic film was formed.
After the heating, the thickness of the organic film on the silicon wafer (film thickness A) was measured. Thereafter, the silicon wafer on which the organic film was formed was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and then air-dried. After the air-drying, the thickness of the organic film on the silicon wafer (film thickness B) was measured.
The remaining rate (%) of the organic film thickness was calculated using the following formula, and the calculated value was shown in the column of "Solvent resistance (unit: %)" in Table 1.
It can be said that the greater the residual thickness rate (%) of the organic film, the more excellent the solvent resistance of the obtained organic film.
Residual rate (%) of organic film thickness=film thickness B/film thickness A×100

[Evaluation of breaking elongation]
Each of the compositions prepared in the Examples and Comparative Examples or the comparative compositions was applied onto a silicon wafer by spin coating to form a resin layer.
The silicon wafer on which the resin layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. The obtained composition layer was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 . After the exposure, the temperature was increased at a rate of 10°C/min under a nitrogen atmosphere, and after reaching 180°C, the layer was heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the organic film was peeled off from the silicon wafer.
The peeled organic film was punched out using a punching machine to prepare a test piece with a sample width of 3 mm and a sample length of 30 mm. The longitudinal elongation of the obtained test piece was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, 25°C, and 65% RH (relative humidity) in accordance with JIS-K6251. The measurement was performed five times for each test piece, and the arithmetic average value of the elongation at which the test piece broke (breaking elongation) in the five measurements is shown in the "breaking elongation (unit %)" column in Table 1.
It can be said that the larger the arithmetic mean value, the better the breaking elongation of the obtained organic film.

From the above results, it is apparent that the organic film according to the present invention has excellent solvent resistance.
The comparative composition according to Comparative Example 1 has an I/A of 2.413 and an I/B of 0.419, which does not satisfy either formula (1) or formula (2). It is clear that the organic film according to Comparative Example 1 has poor solvent resistance.

Next, instead of the resin PA-1 in Example 1, three compositions were used: a closed-ring polyimide resin, a resin containing a polybenzoxazole precursor, or a closed-ring polybenzoxazole. Solvent resistance and breaking elongation were evaluated in the same manner as in Example 1. Regardless of which of the three compositions was used, the solvent resistance and breaking elongation were both at the same level as in Example 1.

<Example 101>
The composition described in Example 1 was applied by spinning to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed so that the film thickness was 20 μm. The composition applied to the resin substrate was dried at 100° C. for 2 minutes, and then exposed using a stepper (Nikon, NSR1505 i6). Exposure was performed through a mask with a square pattern (a square pattern of 100 μm in length and width, repetition number 10) at a wavelength of 365 nm with an exposure dose of 400 mJ/cm ² to produce a square remaining pattern. After exposure, the substrate was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Next, the temperature was increased at a rate of 10° C./min under a nitrogen atmosphere, and after reaching 180° C., the film was heated at this temperature for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. In addition, when a semiconductor device was manufactured using these interlayer insulating films for a redistribution layer, it was confirmed that the device operated without any problems.

Claims (11)

Satisfying at least one formula selected from the group consisting of the following formula (1) and the following formula (2):
It is used as an insulating film for semiconductor devices, an interlayer insulating film for a rewiring layer, a stress buffer film, a sealing film, or a substrate material .
a cured product of a coating film of a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor, and a polybenzoxazole precursor;
The polyimide precursor contains a repeating unit represented by the following formula (2A):
Organic membrane;
Formula (1): I / A ≧ 2.5
Formula (2): I / B ≧ 0.5
In the formula (1) or (2), I is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 , A is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.200 Å ^-1 to 0.300 Å ^-1 , B is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.017 Å ^-1 to 0.025 Å ^-1 , and q is a value defined by the following formula (Q) in small-angle scattering:
Formula (Q): q = (4π/λ) sin θ
In formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam.
In formula (2A), A1 ^and A2 ^each independently represent an oxygen atom or NH, R111 ^represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and R114 ^each independently represent a hydrogen atom or a monovalent organic group, and at least one of R113 ^and R114 ^contains a polymerizable group. Satisfying at least one formula selected from the group consisting of the following formula (1) and the following formula (2):
The resin includes a heterocyclic structure,
a cured product of a coating film of a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor, and a polybenzoxazole precursor;
The polyimide precursor contains a repeating unit represented by the following formula (2A):
Organic membrane;
Formula (1): I / A ≧ 2.5
Formula (2): I / B ≧ 0.5
In the formula (1) or (2), I is the maximum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.030 Å ^-1 to 0.065 Å ^-1 , A is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.200 Å ^-1 to 0.300 Å ^-1 , B is the minimum relative intensity value when small-angle neutron scattering measurement is performed on the organic film with q in the range of 0.017 Å ^-1 to 0.025 Å ^-1 , and q is a value defined by the following formula (Q) in small-angle scattering:
Formula (Q): q = (4π/λ) sin θ
In formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam.
In formula (2A), A1 ^and A2 ^each independently represent an oxygen atom or NH, R111 ^represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and R114 ^each independently represent a hydrogen atom or a monovalent organic group, and at least one of R113 ^and R114 ^contains a polymerizable group. The organic film according to claim 1 or 2 , wherein the composition comprises a thermal base generator. The organic film according to claim 1 or 2, wherein the composition contains a metal element-containing compound. The organic film according to claim 1 or 2 , wherein the composition comprises a Group 4 element-containing compound. The organic film according to claim 1 , wherein the composition comprises an organic compound containing a titanium atom. The composition according to any one of claims 1 to 6 , which is used for forming an organic film. A laminate comprising two or more layers of the organic film according to any one of claims 1 to 6 , and a metal layer between any two adjacent layers of the organic films. A semiconductor device comprising the organic film according to any one of claims 1 to 6 or the laminate according to claim 8 . A method for producing the organic film according to any one of claims 1 to 6 , comprising a film-forming step of applying the composition to a substrate to form a film. The method for producing an organic film according to claim 10 , further comprising the step of heating the film at 50 to 450°C.