JP7204937B2 - Organic film and its manufacturing method, composition, laminate, and semiconductor device - Google Patents

Description

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

The organic film can be formed using a simple film-forming method such as a coating method, a printing method, or a transfer method. In addition, by adjusting the structure of each component (for example, resin) contained in the film, the content of each component contained in the film, etc., it is possible to improve the mechanical properties such as the breaking elongation of the film and the physical properties such as the insulating properties of the film. It is also possible to easily design characteristics and the like. Therefore, in recent years, organic films containing organic materials have been used in various fields as films used in devices for various applications.
For example, organic films containing resins such as polyimide and benzoxazole are applied to various applications because of their excellent heat resistance and insulating properties. The use is not particularly limited, but in the case of a semiconductor device for mounting, it can be used as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.
Industrial applications of such organic films are increasingly expected.

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

WO2017/033833

With the use of organic films in various fields, it is desired to provide organic films with excellent solvent resistance.

The present invention provides an organic film having excellent solvent resistance, a method for producing the same, a composition for forming the organic film, a laminate containing the organic film, and a semiconductor device containing the organic film or the laminate. intended to provide

Examples of representative embodiments of the present invention are 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 the above formula (2), I is the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ for the above organic film. is the maximum value, A is the minimum value of the relative intensity value when q is in the range of 0.200 Å ⁻¹ to 0.300 Å ⁻¹ for the above organic film, and the neutron small angle scattering measurement is performed, and B is the above It is the minimum value of the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.017 Å ⁻¹ to 0.025 Å ⁻¹ for the organic film, and q is the following formula (Q) in small angle scattering. is a value defined by;
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 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 polyimides, polybenzoxazoles, polyimide precursors, and polybenzoxazole precursors. film.
<3> The organic film according to <2>, wherein the composition contains a photosensitizer.
<4> A composition used 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 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 an organic film according to any one of <1> to <3>, comprising a film forming step of applying the composition to a substrate to form a film. Method.
<8> The method for producing an organic film according to <7>, comprising heating the film at 50 to 450°C.

According to the present invention, an organic film having excellent solvent resistance, a method for producing the same, a composition used for forming the organic film, a laminate containing the organic film, and a semiconductor containing the organic film or the laminate A device is provided.

Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
As used herein, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Moreover, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the substrate is referred to as "upper", or when there is a composition layer, the direction from the substrate toward the composition layer is referred to as "upper". , the opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertically upward direction.
In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, 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, the temperature is 23° C. and the pressure is 101,325 Pa (1 atm) unless otherwise specified.
In this specification, 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 formula (1) and formula (2) below.
Formula (1): I/A≧2.5
Formula (2): I/B≧0.5
In the above formula (1) or the above formula (2), I is the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ for the above organic film. is the maximum value, A is the minimum value of the relative intensity value when q is in the range of 0.200 Å ⁻¹ to 0.300 Å ⁻¹ for the above organic film, and the neutron small angle scattering measurement is performed, and B is the above It is the minimum value of the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.017 Å ⁻¹ to 0.025 Å ⁻¹ for the organic film, and q is the following formula (Q) in small angle scattering. is a value defined by
Formula (Q): q = (4π/λ) sin θ
In formula (Q), λ is the neutron beam wavelength (Å), and θ is the neutron beam scattering angle (°).
Also, 1 Å is 0.1 nm.

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

Although the reason why the organic film of the present invention is excellent in solvent resistance is not clear, it is presumed as follows.
Satisfying formula (1) means that q is 0.030 Å with respect to the minimum value A of the relative intensity value when neutron small angle scattering measurement is performed in the range of 0.200 Å ^-1 to 0.300 Å ^-1 . It means that the maximum value I of the relative intensity value when neutron small angle scattering measurement is performed in the range of ^-1 to 0.065 Å ^-1 is 2.5 times or more.
Satisfying formula (2) means that the above maximum value I is equal to the minimum value B of the relative intensity value when neutron small angle scattering measurement is performed in the range of 0.017 Å ⁻¹ to 0.025 Å ⁻¹ q It means 0.5 times or more.
As a result of extensive studies, the present inventors found that the maximum value I in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ for q is 2.5 times or more the minimum value A, or the minimum value It has been found that an organic film that is 0.5 times or more than B or that satisfies both of them has excellent solvent resistance.
Here, the maximum value I of the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ is the arrangement state of the components such as resin contained in the organic film, It is considered that it is a value that changes depending on the association state and the like.
As an example, when the organic film contains a resin having a ring structure (for example, a heterocyclic structure) such as a polyimide resin, for example, if the organic film contains many layers in which the ring structures are stacked, the above maximum It is considered that the value I increases and satisfies at least one selected from the group consisting of the above formulas (1) and (2).
Further, for example, if the organic film contains many 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 uneven, and the resin in the organic film The organic film is considered to be excellent in solvent resistance because of the presence of high-density portions and the like.
Based on the above findings, the present inventors have found that an organic film having excellent solvent resistance can be obtained by satisfying at least one formula selected from the group consisting of formulas (1) and (2). The inventors have found that and completed the present invention.
In addition, due to the interaction between the resins, etc., the organic film satisfies at least one formula selected from the group consisting of formulas (1) and (2), so that the elongation at break is large and the mechanical properties are excellent. It is thought that an organic film with a high density is likely to be obtained.

<Neutron Small Angle Scattering (SANS) Measurement>
Small-angle neutron scattering measurement is performed by the method described in Examples below.
In addition, the relative intensity value in the present invention means a blank cell without a sample (for example, an empty cell not filled with a measurement sample) obtained by performing small-angle neutron scattering measurement on a measurement sample and counting the measured counts from a blank cell. It is the value obtained by subtracting the number of background counts measured using a sample holder).

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

[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, and 2.8 or more. It is more preferably 3.0 or more, particularly preferably 4.0 or more, and most preferably 4.2 or more.
Although the upper limit of the value of I/A is not particularly limited, it may be 100 or less, for example.
The value of I/A is, 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, and the content of each component contained in the organic film. , the method of manufacturing the organic film (eg, curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, and the like.

[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, and preferably 0.65 or more. It is more preferably 0.70 or more, particularly preferably 0.80 or more, and most preferably 0.84 or more.
Although the upper limit of the value of I/B is not particularly limited, it may be 20 or less, for example.
The value of I/B is, 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, and the content of each component contained in the organic film. , the method of manufacturing the organic film (eg, curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, and the like.

[Maximum value I]
The maximum value I when q is in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ should be within the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ , but q is 0.032 Å ⁻ The maximum value I is preferably within the range of ¹ to 0.065 Å ⁻¹ , and more preferably q is within the range of 0.034 Å ⁻¹ to 0.065 Å ⁻¹ . .

[ ^I12 /A, ^I13 /A]
When the organic film of the present invention satisfies the formula (1), it preferably further satisfies the following formula (1-2), 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 the above formula (1-3), I ¹² is the organic film when q is in the range of 0.035 Å ⁻¹ to 0.065 Å ⁻¹ when small angle neutron scattering measurement is performed. I ¹³ is the maximum value of the relative intensity value of the above organic film when performing small angle neutron scattering measurement with q in the range of 0.040 Å ⁻¹ to 0.065 Å ⁻¹ and A and q are synonymous with 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), 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 the above formula (1-3), I ²² is obtained 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 . I ²³ is the maximum value of the relative intensity value when the neutron small angle scattering measurement is performed for the above organic film with q in the range of 0.040 Å ⁻¹ to 0.065 Å ⁻¹ and B and q are synonymous with A and q in Formula (2).

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

The organic film is preferably an organic film formed from a coating film of the composition, more preferably a cured product of the coating film of the composition, and a cured product of the coating film of the composition containing the above resin. More preferably, a coating film of a composition containing at least one resin selected from the group consisting of polyimides, polybenzoxazoles, polyimide precursors and polybenzoxazole precursors (hereinafter also referred to as "specific resin"). is particularly preferred.
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 above-described organic film, or the resin that becomes the resin contained in the above-described organic film in the cured product, such as polyimide, polyimide precursor, polybenzoxazole, And, it is preferably at least one selected from the group consisting of polybenzoxazole precursors, more preferably at least one resin selected from the group consisting of polyimides and polyimide precursors, and is a polyimide precursor It is even more preferable to have

式（２）中、Ａ^１及びＡ^２は、それぞれ独立に、酸素原子又はＮＨを表し、Ｒ^１１１は、２価の有機基を表し、Ｒ^１１５は、４価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表す。[Polyimide precursor]
Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
Formula (2)

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

A ¹ and A ² in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups 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 preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. A group represented by -Ar-L-Ar- is exemplified as a particularly preferred embodiment of the present invention. However, Ar is each independently an aromatic group, 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. Preferred ranges for these are as described above.

R ¹¹¹ is preferably derived from a diamine. Diamines used in the production of polyimide precursors 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, 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 It is preferably a diamine containing, more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:

式中、Ａは、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－、ＮＨＣＯ－、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、又は、－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、又は、－Ｃ（ＣＨ_３）_２－であることが更に好ましい。

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O) -, -S-, -SO ₂ -, NHCO-, or preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -C ( ═O)—, —S—, or —SO ₂ —, more preferably a group selected from —CH ₂ —, —O—, —S—, —SO ₂ —, —C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - is more preferred.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diamino diphenyl 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-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)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-a 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'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4, 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-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)octafluoro Butane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexa Fluoropropane, 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-trifluoro methylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2 -bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino -at least one diamine selected from 2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolyzine and 4,4'-diaminoquaterphenyl is mentioned.

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

Diamines having at least two alkylene glycol units in the main chain are also preferred examples. Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule are more preferred, and diamines containing no aromatic ring are more preferred. 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 (Trade names above, 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® KH-511, ED-600, ED-900, ED-2003, EDR-148 and EDR-176 are shown below.

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

R ¹¹¹ is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film. However, Ar is each independently an aromatic group, 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.

式（５１）中、Ｒ^５０～Ｒ^５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ^５０～Ｒ^５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基である。
Ｒ^５０～Ｒ^５７の１価の有機基としては、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。

式（６１）中、Ｒ^５８及びＲ^５９は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
式（５１）又は（６１）の構造を与えるジアミン化合物としては、２，２’－ジメチルベンジジン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種で又は２種以上を組み合わせて用いてもよい。From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoro is a methyl group.
The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.
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 and the like. These may be used alone or in combination of two or more.

式（５）中、Ｒ^１１２は、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、及びＮＨＣＯ－、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－及びＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、－ＣＯ－、－Ｓ－及びＳＯ_２－からなる群から選択される２価の基であることが更に好ましい。R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
Formula (5)

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

Formula (6)

式（Ｏ）中、Ｒ^１１５は、４価の有機基を表す。Ｒ^１１５の好ましい範囲は式（２）におけるＲ^１１５と同義であり、好ましい範囲も同様である。R ¹¹⁵ specifically includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof 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 synonymous with 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′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 ,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these C1-6 alkyl and C1-6 alkoxy derivatives are included.

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

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes residues of bisaminophenol derivatives.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, more preferably both contain a polymerizable group preferable. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically photopolymerizable 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, an amino groups. A group having an ethylenically unsaturated bond is preferable as the radically polymerizable group possessed by the polyimide precursor or the like.
The group having an ethylenically unsaturated bond includes a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, 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.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. , —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups, and more preferably ethylene, propylene, trimethylene, —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups. A polyalkyleneoxy group is more preferable from the viewpoint of easily satisfying formula (1) or formula (2) in .
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred aspects of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Monovalent organic groups include aromatic groups and aralkyl groups having an acidic group attached to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More 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.
More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes 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 1-30. Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, 2-(2-(2 -ethoxyethoxy)ethoxy)ethoxy)ethoxy group, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy group ) ethoxy groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. is mentioned. Among them, a cyclohexyl group is most preferable from the viewpoint of compatibility with high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group, which will be described later, is preferable.
Specific examples of aromatic groups include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene ring. ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or 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 tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good. Examples of such tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.

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

For the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, the diamine component includes bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

式（２－Ａ）中、Ａ^１及びＡ^２は、酸素原子を表し、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、２価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１１３及びＲ^１１４の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor or the like used in the present invention is preferably 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 represents a hydrogen atom or a monovalent organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and 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 thereof. Further, it may contain a structural isomer of the repeating unit represented by formula (2). Needless to say, the polyimide precursor may also contain other types of repeating structural units in addition to the repeating units of formula (2) above.

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of the total repeating units is a repeating unit represented by formula (2). exemplified.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, still more preferably 22,000 to 25,000. When the composition for forming an organic film of the present invention contains a metal element-containing compound, an aspect in which the weight average molecular weight (Mw) is 22,000 to 26,000 is also preferred. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. When the composition for forming an organic film of the present invention contains a metal element-containing compound, an aspect in which the number average molecular weight (Mn) is 7,200 to 20,000 is also preferred, and in that case, 8,000 to 18 is more preferred. ,000, more preferably 10,000 to 14,000.
The polyimide precursor preferably has a molecular weight distribution of 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. When the composition for forming an organic film of the present invention contains a metal element-containing compound, an aspect in which the molecular weight dispersity is 1.5 or more is also preferable, more preferably 1.7 or more, and more preferably 1.7 or more. 1.8 or more. Although the upper limit of the polyimide precursor molecular weight dispersity is not particularly defined, for example, it is preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, and even more preferably 3.2 or less. It is preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
In the present specification, the molecular weight dispersity 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 a polyimide 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 23° C. by 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.

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

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has silicon atoms.
A silicon atom, for example, is preferably contained in R ¹³¹ in a repeating unit represented by formula (4) described later, and R ¹³¹ in a repeating unit represented by formula (4) described later is an organic modified (poly ) is more preferably contained as a siloxane structure.
The silicon atom or the organically modified (poly)siloxane structure may be contained in the 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 polyimide is preferably 0.01 to 5 mol/g, 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 its main chain or in a side chain, preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹³² in a repeating unit represented by the formula (4) described later, or R ¹³¹ in a repeating unit represented by the formula (4) described later. It is more preferably included as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by (4) or R ¹³¹ in the repeating unit represented by formula (4) described below.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described ^later , and ethylene It is more preferably included as a group having a polyunsaturated bond.
The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).

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

In formula (IV), R ²¹ is 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, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.

式（Ｒ１）～（Ｒ３）中、Ｌは単結合、又は、炭素数２～１２のアルキレン基、炭素数２～３０の（ポリ）アルキレンオキシ基若しくはこれらを２以上結合した基を表し、Ｘは酸素原子又は硫黄原子を表し、＊は他の構造との結合部位を表し、●は式（ＩＩＩ）中のＲ^２０１が結合する酸素原子との結合部位を表す。
式（Ｒ１）～（Ｒ３）中、Ｌにおける炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様は、上述のＲ^２１における、炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様と同様である。
式（Ｒ１）中、Ｘは酸素原子であることが好ましい。
式（Ｒ１）～（Ｒ３）中、＊は式（ＩＶ）中の＊と同義であり、好ましい態様も同様である。
式（Ｒ１）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物（例えば、２－イソシアナトエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ２）で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物（例えば、２－ヒドロキシエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ３）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物（例えば、グリシジルメタクリレート等）とを反応することにより得られる。Among these, R ²¹ is preferably a group represented by any one of the following formulas (R1) to (R3), 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 combined, and 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) bonds.
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R ²¹ having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
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 (eg, 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 (e.g., glycidyl methacrylate, etc.) can get.

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

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

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

- Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Also, 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.
Further, 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 2 to 35 mgKOH/g, and 3 to 30 mgKOH. /g is more preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
Considering the dissociation reaction in which hydrogen ions are released from an acid, the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, the values listed in the Chemical Society of Japan, Revised 5th Edition, Basics of Chemistry, may be referred to.
Also, 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 selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.

-Phenolic hydroxy group-
The polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
Polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably contained in, for example, R ¹³² in a repeating unit represented by formula (4) described later or R ¹³¹ in a repeating unit represented by formula (4) described later.
The amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.

式（４）中、Ｒ^１３１は、２価の有機基を表し、Ｒ^１３２は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３１及びＲ^１３２の少なくとも一方に位置していてもよいし、下記式（４－１）又は式（４－２）に示すようにポリイミドの末端に位置していてもよい。
式（４－１）

式（４－１）中、Ｒ^１３３は重合性基であり、他の基は式（４）と同義である。
式（４－２）

Ｒ^１３４及びＲ^１３５の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式（４）と同義である。The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), represented by the formula (4) A compound containing a repeating unit and having a polymerizable group is more preferable.
Formula (4)

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

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

The polymerizable group is synonymous with the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group are the same as those of R ¹¹¹ in formula (2), and the preferred range is also the same.
R ¹³¹ also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferably a diamine residue containing no aromatic ring.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (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.

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

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

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

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

For the purpose of improving 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, the main chain end of the polyimide may be blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, or the like. preferable. Among these, it is more preferable to use monoamines, 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-aminobenzenesulfone acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. 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.

-Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100

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

For polyimide, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid A method of reacting a diamine compound with a diamine compound, a method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a monoactive ester compound, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent with a tetracarboxylic dianhydride and an alcohol to obtain a diester, then acid chloride the remaining dicarboxylic acid, diamine (a part of which is a monoamine Substitution with a terminal blocking agent) is used to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or imide in the middle Synthesis using a method of terminating the polymerization reaction and partially introducing an imide structure, or a method of partially introducing an imide structure by blending a completely imidized polymer with its polyimide precursor. can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).

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

式（３）中、Ｒ^１２１は、２価の有機基を表し、Ｒ^１２２は、４価の有機基を表し、Ｒ^１２３及びＲ^１２４は、それぞれ独立に、水素原子又は１価の有機基を表す。[Polybenzoxazole precursor]
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
Formula (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. show.

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

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. 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, and 4 to 15 is more preferred, and 5-10 is particularly preferred. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing linear aliphatic groups 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, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, thoria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

（式中、Ｚは炭素数１～６の炭化水素基であり、ｎは１～６の整数である。）

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

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

式中、Ａは－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、及び、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。

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

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic 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 the above formula (2), and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. -diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino- 4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-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, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination.

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

式中、Ｘ_１は、－Ｏ－、－Ｓ－、－Ｃ（ＣＦ_３）_２－、－ＣＨ_２－、－ＳＯ_２－、－ＮＨＣＯ－を表す。

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

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc). _R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom _, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

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

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

In the above formula (A-s), the ortho position of the phenolic hydroxyl group, that is, having a substituent also at R ₃ is thought to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and cured at a low temperature. It is particularly preferable in that the effect of increasing the cyclization rate is further increased.

Further, in the above formula (A-s), when R ₂ is an alkyl group and R ₃ is an alkyl group, high transparency to the i-line and high cyclization rate when cured at a low temperature are said to be obtained. It is preferable because the effect can be maintained.

Further, in formula (As) above, it is more preferred that R ₁ is alkylene or 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 2CH ₃ )-, -CH(CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₃ )- _, -C (CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH ₂ CH(CH ₃ ) ₂ )-, -CH _{( CH2CH2CH2CH2CH3} ) _{- , -C ( CH3 ) ( CH2CH2CH2CH2CH3 ) - , -CH ( CH2CH2CH2CH2CH2CH3 )} -, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, among which -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) _2- is a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and high cyclization rate when cured at low temperature. It is more preferable in that it can be obtained.

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

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-A-2013-256506, the contents of which are incorporated herein. incorporated into. Of course, it goes without saying that they are not limited to these.

The polybenzoxazole precursor may also contain other types of repeating structural units in addition to the repeating units of formula (3) above.
It is preferable to contain a diamine residue represented by the following formula (SL) as another type of repeating structural unit from the viewpoint of suppressing the occurrence of warping due to ring closure.

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

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, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms. At least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of a structure and b structure may be block polymerization or random polymerization. The mol % of the Z moiety is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.

In formula (SL), preferred Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. Further, 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 in the above range, it is possible to more effectively lower the elastic modulus after dehydration ring closure of the polybenzoxazole precursor, and to achieve both the effect of suppressing warpage and the effect of improving solvent solubility.

When containing a diamine residue represented by formula (SL) as another type of repeating structural unit, further, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as a repeating structural unit It is also preferred to include Examples of such tetracarboxylic acid residues include those of R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when used in the composition described later, is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further Preferably it is 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.

式（Ｘ）中、Ｒ^１３３は、２価の有機基を表し、Ｒ^１３４は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３３及びＲ^１３４の少なくとも一方に位置していてもよいし、下記式（Ｘ－１）又は式（Ｘ－２）に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式（Ｘ－１）

式（Ｘ－１）中、Ｒ^１３５及びＲ^１３６の少なくとも一方は、重合性基であり、重合性基でない場合は有機基であり、他の基は式（Ｘ）と同義である。
式（Ｘ－２）

式（Ｘ－２）中、Ｒ^１３７は重合性基であり、他は置換基であり、他の基は式（Ｘ）と同義である。[Polybenzoxazole]
Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.

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

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

The polymerizable group is synonymous with the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.

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

R ¹³⁴ represents a tetravalent organic group. Tetravalent organic groups include examples of R ¹²² in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² combine with 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, it forms the structure below.

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

The polybenzoxazole may contain repeating structural units of the above formula (X) that all contain one type of R ¹³¹ or R ¹³² , and the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² It may contain a repeating unit of X). Moreover, the polybenzoxazole may also contain other types of repeating structural units in addition to the repeating units of the above formula (X).

Polybenzoxazole is obtained by, for example, 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 obtained by oxazolating it using a known oxazolating reaction method.
In the case of dicarboxylic acid, in order to increase the reaction yield, etc., an active ester type dicarboxylic acid derivative pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.

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

[Method for producing polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
Polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promoting the cyclization reaction by acting a catalyst), or directly , polyimide may be synthesized.

-Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, terminal blockers such as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds are used to block the ends of polyimide precursors. Sealing is preferred. As the terminal blocker, 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-amino naphthalene, 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 and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation-
A step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor or the like is soluble, so that solid deposition can be performed.
Thereafter, the polyimide precursor or the like is dried to obtain a powdery 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, and more preferably 40% by mass or more relative to the total solid content of the composition. Preferably, it is more preferably 50% by mass or more. Further, 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, and 98% by mass or less, relative to the total solid content of the composition. is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one resin, or may contain two or more resins. When two or more types are included, the total amount is preferably within the above range.

<Other resins>
The composition of the present invention may contain the specific resin described above and other resin (hereinafter also simply referred to as "other resin") different from the specific resin.
Other resins include polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, and siloxane structures that are different from the specific resins. Examples thereof include resins containing the resin, acrylic resins, and the like.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, by adding an acrylic resin having a high polymerizable group value having a weight average molecular weight of 20,000 or less to the composition, the composition It is possible to improve the applicability of a substance, the solvent resistance of an organic film, and the like.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the composition. more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more .
In addition, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass, based on the total solid content of the composition. It is more preferably 60% by mass or less, and even more preferably 50% by mass or less.
In addition, as a preferred embodiment of the composition of the present invention, the content of other resins may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, relative to the total solid content of the composition. More preferably, it is 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited as long as it is 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 included, the total amount is preferably within the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitizer.
A photopolymerization initiator is preferable as the photosensitive agent.

[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 radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action 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 formulas (1) and (2), the composition of the present invention is used as a radical photopolymerization initiator, which will be described later. It preferably contains a metal element-containing compound. That is, in the present invention, among the metal element-containing compounds described later, those having radical polymerization initiation ability can be used as the radical photopolymerization initiator.
Here, having the ability to initiate radical polymerization means being able to generate free radicals capable of initiating radical polymerization. For example, for a composition containing a radically polymerizable monomer, a binder polymer, and a metal element-containing compound, a wavelength range in which the metal element-containing compound absorbs light and the radically polymerizable monomer does not absorb light. The presence or absence of polymerization initiation ability can be confirmed by confirming the presence or absence of disappearance of the radically polymerizable monomer when irradiated with light. In order to confirm the presence or absence of disappearance, an appropriate method can be selected according to the type of the radically polymerizable monomer and the binder polymer. good.

When the composition of the present invention contains a metal element-containing compound or the like having radical polymerization initiation ability, the composition of the present invention preferably does not substantially contain a radical polymerization initiator other than the metal element-containing compound. Substantially containing no 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 equal to the metal element-containing compound. is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass, relative to the total mass of
Further, when the composition of the present invention contains a metal element-containing compound having radical polymerization initiation ability, etc., the composition of the present invention may contain the above-mentioned metal element-containing compound and another radical photopolymerization initiator. preferable.
When the composition of the present invention contains a metal element-containing compound and another photoradical polymerization initiator, the content of the metal element-containing compound with respect to the total content of the metal element-containing compound and the other photoradical polymerization initiator The amount is preferably 20-80% by mass, more preferably 30-70% by mass.
Further, as the other radical photopolymerization initiator, an oxime compound described later is preferable.

The photoradical polymerization initiator is a compound having a molar extinction coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the range of about 300 to 800 nm (preferably 330 to 500 nm),
It is preferable to contain at least one type. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the radical photopolymerization initiator, any known compound can be used. 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 oxide, hexaarylbiimidazole, oxime derivatives, etc. oxime compounds, 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. mentioned. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein.

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

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the radical photopolymerization initiator. 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.

As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, which has a maximum absorption wavelength matched to a wavelength light source such as 365 nm or 405 nm, can also be used.

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

Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF). The metallocene compound includes a metal element-containing compound described later and having the ability to initiate radical polymerization.

As the radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

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

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-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 the radical photopolymerization initiator. An oxime-based photopolymerization initiator has a >C=N--O--C(=O)-- linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP 2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

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

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

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.

More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, more preferably metallocene compounds or oxime compounds, and oxime compounds. is even more preferred.

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

In formula (I), R ¹⁰⁰ 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, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms; a phenyl group substituted with at least one of an alkyl group of 18 and an alkyl group having 1 to 4 carbon atoms, or biphenyl, and R ^I01 is a group represented by formula (II) or the same as R ^I00 and each of R ¹⁰² to R ¹⁰⁴ is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or halogen.

In the formula, R ¹⁰⁵ to R ¹⁰⁷ are the same as R ¹⁰² to R ¹⁰⁴ in formula (I) above.

Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used.

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

[Photoacid generator]
Moreover, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing a photoacid generator, for example, an acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developer (for example, alkaline aqueous solution) increases, and the exposed portion is removed by the developer. A positive relief pattern that is removed can be obtained.
Further, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed area accelerates the cross-linking reaction of the polymerizable compound, It is also possible to adopt a mode in which the exposed area is more difficult to be removed by the developer than the non-exposed area. According to such an aspect, a negative relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid upon exposure, and includes quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, onium salt compounds such as iodonium salts, imidosulfonates, and oximes. Sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate can be used.

The quinonediazide compounds include polyhydroxy compounds in which the sulfonic acid of quinonediazide is ester-bonded, polyamino compounds in which the sulfonic acid of quinonediazide is sulfonamide-bonded, and polyhydroxypolyamino compounds in which the sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded. and those bound by at least one of In the present invention, for example, it is preferable that 50 mol % or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, or a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound may be contained. may contain.

The naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity and film retention rate are further improved.
Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts and ester compounds of these compounds, and the like. be done.

Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, you may use a commercial item as a photo-acid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all from Fujifilm manufactured by Kojunyaku Co., Ltd.) and the like.

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

式（Ｐ）中、Ｍは、第４族元素であり、Ｒは、それぞれ独立に、置換基である。
上記Ｒは、それぞれ独立に、芳香族基、アルキル基、ハロゲン原子及びアルキルスルホニルオキシ基から選択されることが好ましい。<Metal element-containing compound>
The composition of the present invention preferably further contains a metal element-containing compound.
From the viewpoint of further improving solvent resistance, the metal element-containing compound in the present invention is preferably the photoradical polymerization initiator.
The metal element-containing compound is preferably an organic substance containing a metal element. That is, it is preferably an organometallic compound.
Further, the metal element in the metal element-containing compound in the present invention includes iron, palladium, nickel, Group 4 elements, etc., with Group 4 elements being preferred.
That is, the metal element-containing compound is preferably a Group 4 element-containing compound, 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 a titanium atom, a zirconium atom and a hafnium atom, and at least one selected from the group consisting of a titanium atom and a zirconium atom. More preferred are organic compounds containing one, and even more preferred are organic compounds containing a titanium atom. Further, the organic compound containing at least one selected from a titanium atom and a zirconium atom is preferably an organic compound containing an organic group and a titanium atom or a zirconium atom, and the titanium atom contained in one molecule of the organic compound. and the total number of zirconium atoms is preferably one. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom. Preferred heteroatoms are oxygen, sulfur and nitrogen atoms.
In the present invention, at least one of the organic groups is preferably a cyclic group, more preferably at least two are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, more preferably a 5-membered cyclic group. As the five-membered cyclic group, a cyclopentadienyl group is preferred. Further, the organotitanium compound or the like 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 preferable, and a titanium atom and a zirconium atom are more preferable.

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

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 represents an organometallic compound having two substituted cyclopentadienyl anion derivatives as η5-ligands, and includes titanocene derivatives, zirconocene derivatives, hafnocene derivatives and the like.
Further, the Group 4 element-containing compound used in the present invention is preferably selected from titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds, and titanocene compounds and zirconocene compounds. and hafnocene compounds, more preferably selected from titanocene compounds and zirconocene compounds.
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 at least one selected from the group consisting of titanocene and titanocene derivatives. It is more preferable to have

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 Group 4 element-containing compounds include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, and The following compounds are exemplified.

Further, among the Group 4 element-containing compounds, organic compounds containing a titanium atom include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopenta Dienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1- yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclo Pentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl-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-(pyri-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfonamide ) 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(cyclopenta) dienyl)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-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)-sulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(pyrrolidin-2,5-dion-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-dimethyl-3-pyrrolidine-2, 5-dio-1-yl)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-((2-chloroethoxy)-carbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenoxy carbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylthioureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(3-butylthioureido)phenyl]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(cyclopenta dienyl)bis[2,6-difluoro-3-(3,3-dimethylureido)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-ethylhexanoyl amino) 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 (Cyclopentadienyl)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-xyloylamino)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-isobutyl thylbenzoylamino)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, 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-dimethyl butanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4-dimethylpentyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclo pentadienyl)bis[2,6-difluoro-3-((4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylpenta noylamino)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-allylacetyl amino) 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- isopropylbenzoylamino)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-cyclohexylmethyl-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzoylamino)phenyl]titanium, bis(cyclo pentadienyl)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-dimethylpenta) noylamino)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-3-(N-cyclohexylmethyl-(2-ethyl-2-methyl heptanoyl)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, 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-azetidinon-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-di Fluoro-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-chloropropane noyl)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-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(cyclopenta) dienyl)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(cyclopenta dienyl)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(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-ethylpropionyl amino)phenyl]titanium, bis(trimethylsilylpentadienyl)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(cyclopenta dienyl)bis[2,6-difluoro-3-(3-ethoxymethyl-3-methyl-2-azetidinon-1-yl)phenyl]titanium, bis(cyclope thadienyl)bis[2,6-difluoro-3-(3-allyloxymethyl-3-methyl-2-azetidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(3-chloromethyl-3-methyl-2-azetidinon-1-yl)phenyl]titanium, 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-pyrrolidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl) enyl)bis[2,6-difluoro-3-(6,6-diphenyl-2-piperidino-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N -(2,3-dihydro-1,2-benzothiazol-3-one(1,1-dioxido)-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-chloro benzoyl)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)benzoylamino)phenyl]titanium, 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 (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] phenyl]titanium and the like can also be used.

Among the Group 4 element-containing compounds, 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, (methylcyclopenta dienyl)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)dimethylhydridozirconium, (cyclopentadienyl)triethoxyzirconium, (cyclopentadienyl)triisopropoxyzirconium, (cyclopentadienyl)triphenoxyzirconium, (cyclo pentadienyl)dimethylisopropoxyzirconium, (cyclopentadienyl)diphenylisopropoxyzirconium, (cyclopentadienyl)dimethoxychlorozirconium, (cyclopentadienyl)methoxydichloro Zirconium, (Cyclopentadienyl)diphenoxychlorozirconium, (Cyclopentadienyl)phenoxydichlorozirconium, (Cyclopentadienyl)tri(phenyldimethylsilyl)zirconium, (n-butylcyclopentadienyl)dimethyl n-butoxy Zirconium, (benzylcyclopentadienyl)di-m-tolylmethylzirconium, (trifluoromethylcyclopentadienyl)tribenzylzirconium, (diphenylcyclopentadienyl)dinorbornylmethylzirconium, (tetraethylcyclopentadienyl) tribenzylzirconium, (pentatrimethylsilylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)thrineopentylzirconium, (pentamethylcyclopentadienyl)methyldichlorozirconium, (pentamethylcyclopentadienyl)tri Ethoxyzirconium, (pentamethylcyclopentadienyl)triphenoxyzirconium, (pentamethylcyclopentadienyl)methoxydichlorozirconium, (pentamethylcyclopentadienyl)diphenoxychlorozirconium, (pentamethylcyclopentadienyl)phenoxydichloro zirconium, (indenyl)trimethylzirconium, (indenyl)tribenzylzirconium, (indenyl)trichlorozirconium, (indenyl)trimethoxyzirconium,

(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)chlorohydridozirconium, bis(methylcyclopentadienyl)dimethylzirconium , bis(methylcyclopentadienyl)dibenzylzirconium, bis(methylcyclopentadienyl)dichlorozirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium, bis(pentamethylcyclopentadienyl)dibenzylzirconium, bis (Pentamethylcyclopentadienyl)dichlorozirconium, bis(pentamethylcyclopentadienyl)chloromethylzirconium, bis(pentamethylcyclopentadienyl)hydridomethylzirconium, (cyclopentadienyl)(pentamethylcyclopentadienyl) ) dimethylzirconium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)di-m-tolylzirconium, bis(cyclopentadienyl)di-p-tolylzirconium, bis(cyclopentadienyl)bis (diphenylmethyl)zirconium, bis(cyclopentadienyl)dibromozirconium, bis(cyclopentadienyl)methylchlorozirconium, bis(cyclopentadienyl)ethylchlorozirconium, bis(cyclopentadienyl)cyclohexylchlorozirconium, bis (Cyclopentadienyl)phenylchlorozirconium, bis(cyclopentadienyl)benzylchlorozirconium, bis(cyclopentadienyl)hydridomethylzirconium, bis(cyclopentadienyl)methoxychlorozirconium,

Bis(cyclopentadienyl)ethoxychlorozirconium, bis(cyclopentadienyl)(trimethylsilyl)methylzirconium, bis(cyclopentadienyl)bis(trimethylsilyl)zirconium, bis(cyclopentadienyl)(triphenylsilyl)methyl Zirconium, bis(cyclopentadienyl)(tris(dimethylsilyl)silyl)methylzirconium, bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium, bis(methylcyclopentadienyl)diphenylzirconium, bis(ethyl) 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( trimethylsilylcyclopentadienyl)dimethylzirconium, bis(trimethylsilylcyclopentadienyl)dichlorozirconium, bis(trimethylgermylcyclopentadienyl)dimethylzirconium, bis(trimethylgermylcyclopentadienyl)diphenylzirconium, bis(trimethylstane) nylcyclopentadienyl)dimethylzirconium, bis(trimethylstannylcyclopentadienyl)dibenzylzirconium, bis(trifluoromethylcyclopentadienyl)dimethylzirconium zirconium, bis(trifluoromethylcyclopentadienyl)dinorbornylzirconium, bis(indenyl)dibenzylzirconium, bis(indenyl)dichlorozirconium, bis(indenyl)dibromozirconium, bis(tetrahydroindenyl)dichlorozirconium, Bis(fluorenyl)dichlorozirconium, (propylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)dibenzylzirconium, (pentatrimethylsilylcyclopentadienyl) ( Cyclopentadienyl)dimethylzirconium, (trifluoromethylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)dichlorozirconium, ethylenebis(tetrahydroindenyl)dimethyl Zirconium, ethylenebis(tetrahydroindenyl)dichlorozirconium, dimethylsilylenebis(cyclopentadienyl)dimethylzirconium, dimethylsilylenebis(cyclopentadienyl)dichlorozirconium, isopropylidene(cyclopentadienyl)(9-fluorenyl)dimethyl Zirconium, 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, dimethylsilylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, dimethylsilylenebis(2,3,5-trimethylcyclopenta dienyl)dimethylzirconium, dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium, dimethylsilylenebis(indenyl)dichlorozirconium, methylenebis( cyclopentadienyl)dimethylzirconium, methylenebis(cyclopentadienyl)di(trimethylsilyl)zirconium,

methylene(cyclopentadienyl)(tetramethylcyclopentadienyl)dimethylzirconium, methylene(cyclopentadienyl)(fluorenyl)dimethylzirconium, ethylenebis(cyclopentadienyl)dimethylzirconium, ethylenebis(cyclopentadienyl) dibenzylzirconium, ethylenebis(cyclopentadienyl)dihydridozirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylchlorozirconium, ethylenebis(tetrahydroindenyl)dibenzylzirconium, isopropylidene (cyclopentadiene) enyl)(methylcyclopentadienyl)dichlorozirconium, isopropylidene(cyclopentadienyl)(octahydrofluorenyl)dihydridozirconium, dimethylsilylenebis(cyclopentadienyl)dineopentylzirconium, dimethylsilylenebis(cyclo pentadienyl)dihydridozirconium, dimethylsilylenebis(methylcyclopentadienyl)dichlorozirconium, dimethylsilylenebis(dimethylcyclopentadienyl)dichlorozirconium, dimethylsilylenebis(tetrahydroindenyl)dichlorozirconium, dimethylsilylene(cyclopentadienyl)dichlorozirconium dienyl)(fluorenyl)dichlorozirconium, dimethylsilylene(cyclopentadienyl)(fluorenyl)dihydridozirconium, dimethylsilylene(methylcyclopentadienyl)(fluorenyl)dihydridozirconium, dimethylsilylenebis(3-trimethylsilylcyclopentadiene) Enyl)dihydridozirconium, dimethylsilylenebis(indenyl)dimethylzirconium, diphenylsilylenebis(indenyl)dichlorozirconium, phenylmethylsilylenebis(indenyl)dichlorozirconium, and compounds in which the zirconium atoms of these compounds are substituted with hafnium atoms, etc. can also

In addition, compounds containing an iron atom, a palladium atom, a nickel atom, or the like can be used as the metal element-containing compound.
As the compound containing an iron atom, a complex compound containing an iron atom is preferable, and a metallocene compound such as ferrocene is more preferable.
A complex compound containing a palladium atom or a nickel atom is more preferable as the compound containing a palladium atom or a nickel atom.
A compound containing an iron atom, a palladium atom, a nickel atom, or the like may or may not have the ability to initiate radical polymerization, but preferably has the ability to initiate radical polymerization.

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, still 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.
1 type(s) or 2 or more types can be used for a metal element containing compound. When two or more kinds are used, the total amount is preferably within the above range.

Further, 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 later is such that the metal element-containing compound: onium salt or other thermal base generator The agent ratio is preferably 99:1 to 1:99, more preferably 90:10 to 10:90, and more preferably 40:60 to 20:80. Such a range makes it possible to achieve a higher ring closure rate at low temperatures and a higher glass transition temperature of the precursor.

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

The number of radically polymerizable groups possessed by the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and may have three or more radically polymerizable groups. more preferred. The upper limit is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less.

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, still 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 difunctional or higher radically polymerizable compound containing two or more radically polymerizable groups, and at least one trifunctional or higher radically polymerizable compound. More preferably, it contains seeds. It may also be a mixture of a difunctional radically polymerizable compound and a trifunctional or higher radically polymerizable compound. For example, the number of functional groups of a difunctional or higher polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of the radically polymerizable compound 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 They are 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 a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is 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 halogeno groups Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as , or tosyloxy group with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

The radically polymerizable compound is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples 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 and trimethylolethane. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth)acryl Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.

Further, as preferred radically polymerizable compounds other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups having and cardo resins.

Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid compounds and the like can also be mentioned. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

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

Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a radical polymerizable compound.

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

Examples of radically polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku ( Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa ( meth) acrylate (as a commercial product KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene glycol residues Structures that are linked via are preferred. These oligomeric types can also be used.

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

Examples of radically polymerizable compounds include urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. , JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A radically polymerizable compound having a group is more preferred. Particularly preferably, in a radically polymerizable compound obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta A compound that is erythritol. Commercially available products include, for example, M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. If the acid value of the radically polymerizable compound is within the above range, the handleability in production is excellent, and further, the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.

In the composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the organic film. Monofunctional radically polymerizable compounds include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl ( (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) 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 radically polymerizable compound, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

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

-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-
Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group are preferably compounds represented by the following formulas (AM1), (AM4) or (AM5).

（式中、ｔは、１～２０の整数を示し、Ｒ^１０４は炭素数１～２００のｔ価の有機基を示し、Ｒ^１０５は、－ＯＲ^１０６又は、－ＯＣＯ－Ｒ^１０７で示される基を示し、Ｒ^１０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^１０７は、炭素数１～１０の有機基を示す。）

（式中、Ｒ^４０４は炭素数１～２００の２価の有機基を示し、Ｒ^４０５は、－ＯＲ^４０６又は、－ＯＣＯ－Ｒ^４０７で示される基を示し、Ｒ^４０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^４０７は、炭素数１～１０の有機基を示す。）

（式中ｕは３～８の整数を示し、Ｒ^５０４は炭素数１～２００のｕ価の有機基を示し、Ｒ^５０５は、－ＯＲ^５０６又は、－ＯＣＯ－Ｒ^５０７で示される基を示し、Ｒ^５０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^５０７は、炭素数１～１０の有機基を示す。）

(Wherein, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and 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.)

(Wherein, 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 , and R ⁴⁰⁶ represents a hydrogen atom or carbon represents 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 represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ . , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

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

Further, 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 (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Chemical Industry Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 and NIKALAC MW-100LM (these are 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 cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing of the composition and for suppressing warpage.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus is further lowered, and warping can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include 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; Epoxy group-containing silicones such as (oxypropyl)siloxane, etc., but not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, manufactured by ADEKA Corporation), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and being excellent in heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Ricaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

-Oxetane compound (compound having an oxetanyl group)-
The oxetane compounds 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 and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or You may mix 2 or more types.

-Benzoxazine compound (compound having a benzoxazolyl group)-
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.

Preferable examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac dihydrobenzoxazine oxazine 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 60% by mass or less with respect to the total solid content of the composition of the present invention. More preferably, the lower limit is 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.

The polymerizable compounds may be used singly or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

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

Esters such as 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 alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropion methyl acid and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Suitable examples include propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.

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

Suitable sulfoxides include, for example, dimethyl sulfoxide.

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

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

In the present invention, 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- 1 solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably an amount such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. The amount is preferably 10 to 70% by mass, more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating and the method of application.

Only one kind of solvent may be contained, or two or more kinds may be contained. When two or more solvents are contained, the total amount is preferably within the above range.

<Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, in particular a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates 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 be advanced in the heating step described later, so that the solvent resistance can be further improved.

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

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

<Thermal acid generator>
The compositions of the present invention may also contain a thermal acid generator.
The thermal acid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, epoxy compounds, oxetane compounds and benzoxazine compounds. have the effect of making

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, no acid is generated during drying (prebaking: about 70 to 140°C) after coating the composition on a substrate, and the composition is then exposed and developed for patterning and then final heating (curing: about 100 to 400°C). It is preferable to select an acid-generating agent as the thermal acid generator, because it 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 up to 500° C. in a pressure-resistant capsule at 5° C./min.
Equipment used for measuring the thermal decomposition initiation temperature includes Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or trifluoromethane. Haloalkyl sulfonic acids, such as sulfonic acids, and the like are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, those that generate C 1-4 alkylsulfonic acids and C 1-4 haloalkylsulfonic acids are more preferable, and methanesulfonic acid. (4-hydroxyphenyl)dimethylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl methanesulfonate (4-((methoxy carbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, (4- ((Methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl) Propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane, is preferred as the thermal acid generator.

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

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 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. From the viewpoint of electrical insulation of the organic film, it 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 compositions of the invention preferably contain an onium salt.
In particular, when a polyimide precursor is included as another resin, the composition preferably includes an onium salt.
Although the type of onium salt is not particularly limited, ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts are preferred.
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 polymers.

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

The onium salt used in the present invention may be a thermal base generator.
A thermal base generator is a compound that generates a base upon heating, and includes, for example, 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.

式（１０１）中、Ｒ^１～Ｒ^４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^１～Ｒ^４の少なくとも２つはそれぞれ結合して環を形成してもよい。-Ammonium cation-
Preferred ammonium cations are quaternary ammonium cations.
Moreover, as the ammonium cation, a cation represented by the following formula (101) is preferable.

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 combine to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. 12 aryl groups are more preferred. R ¹ to R ⁴ may have substituents, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, arylcarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned.
When at least two of R ¹ to R ⁴ each combine to form a ring, the ring may contain a heteroatom. A nitrogen atom is mentioned as said hetero atom.

The ammonium cation is preferably represented by either formula (Y1-1) or (Y1-2) below.

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

－Anion－
The anion in the ammonium salt is preferably one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions, and carboxylate anions are more preferable because both salt stability and thermal decomposition can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability and developability of the composition can be further improved. In particular, the use of a divalent carboxylic acid anion can further improve the stability, curability and developability of the composition.

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

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

In the present embodiment, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described in Yuho Tsuno Review, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include a CF ₃ group (σm=0.43), a CF ₃ C(=O) group (σm=0.63), and an HC≡C group (σm=0. 21), CH ₂ =CH group (σm = 0.06), Ac group (σm = 0.38), MeOC(=O) group (σm = 0.37), MeC(=O)CH=CH group ( σm=0.21), PhC(=O) group (σm=0.34), H ₂ NC(=O)CH ₂ group (σm=0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒ^ｘ１～Ｒ^ｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシ基又はカルボキシ基を表し、Ａｒは芳香族基を表す。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

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

式（ＸＡ）において、Ｌ^１０は、単結合、又は、アルキレン基、アルケニレン基、芳香族基、－ＮＲ^Ｘ－及びこれらの組み合わせよりなる群から選ばれる２価の連結基を表し、Ｒ^Ｘは、水素原子、アルキル基、アルケニル基又はアリール基を表す。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 a combination thereof, and R ^X is , represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt as an anion has a conjugate acid preferably contains anions with a pKa (pKaH) of 2.5 or less, more preferably 1.8 or less.
The lower limit of the pKa is not particularly limited, but it is preferably -3 or more, and -2 or more from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific resin is improved. is more preferred.
The above pKa is determined according to 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, RMC et al; Oxford, Clarendon Press, 1959). can be done. For compounds not described in these documents, values calculated from structural formulas using software ACD/pKa (manufactured by ACD/Labs) are used.

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

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

-iminium cation-
Preferred iminium cations are pyridinium cations.
As the iminium cation, a cation represented by the following formula (102) is also preferable.

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 each combine to form a ring. may be formed.
In formula (102), R ⁵ and R ⁶ have the same definitions as R ¹ to R ⁴ in formula (101) above, and preferred embodiments are also the same.
In formula (102), R ⁷ preferably combines with at least one of R ⁵ and R ⁶ to form a ring. The ring may contain heteroatoms. A nitrogen atom is mentioned as said hetero atom. Moreover, as said ring, a pyridine ring is preferable.

式（Ｙ１－３）～（Ｙ１－５）において、Ｒ^１０１は、ｎ価の有機基を表し、Ｒ^５は式（１０２）におけるＲ^５と同義であり、Ｒ^７は式（１０２）におけるＲ^７と同義であり、ｎは１以上の整数を表し、ｍは０以上の整数を表す。
式（Ｙ１－３）において、Ｒ^１０１は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からｎ個の水素原子を除いた基であることが好ましく、炭素数２～３０の飽和脂肪族炭化水素、ベンゼン又はナフタレンからｎ個の水素原子を除いた基であることがより好ましい。
式（Ｙ１－３）において、ｎは１～４であることが好ましく、１又は２であることがより好ましく、１であることが更に好ましい。
式（Ｙ１－５）において、ｍは０～４であることが好ましく、１又は２であることがより好ましく、１であることが更に好ましい。The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).

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

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

[Sulfonium salt]
In the present invention, a sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, 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, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
R ⁸ to R ¹⁰ 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, and 6 to 12 carbon atoms. is more preferably an aryl group, 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, and an aryloxy group. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 1 carbon atoms More preferably it has 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

-Iodonium cation-
As the iodonium cation, a diaryliodonium cation is preferred.
Moreover, as the iodonium cation, a cation represented by the following formula (104) is preferable.

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, and 6 to 12 carbon atoms. is more preferably an aryl group, 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 aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

-Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations.
Moreover, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group,
It is more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and even 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, and an aryloxy group. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably 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% 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, still more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
One or two or more onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Thermal base generator>
The composition of the present invention may contain a thermal base generator.
In particular, when the composition contains a polyimide precursor as another resin, the composition preferably contains a thermal base generator.
The thermal base generator may be a compound corresponding to the onium salt described above, or may be a thermal base generator other than the onium salt described above.
Other thermal base generators include nonionic thermal base generators.
Nonionic thermal base generators 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 having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, 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-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

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

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb ¹ and Rb ² may combine with each other to form a ring. The ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb ¹ and Rb ² are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. is preferably a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent, more preferably having a substituent A cyclohexyl group, which may be

Rb ³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms). 23 is preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). Among them, a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. Rb ³ may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by Formula (B1) is preferably a compound represented by Formula (B1-1) or Formula (B1-2) below.

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

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

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

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

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

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, 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 compounds that 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 two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

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

Migration inhibitors are not particularly limited, but heterocyclic rings (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), compounds having thioureas and sulfanyl groups, hindered phenol compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based 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 traps anions such as halogen ions can also be used.

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

Specific examples of migration inhibitors include the following compounds.

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

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

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

Polymerization inhibitors include, for example, 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 , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 - nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, Bis(4-hydroxy-3,5-tert-butyl)phenylmethane and the like are preferably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

Also, the following compounds can be used (Me is a methyl group).

When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition of the present invention, and 0.02 It is more preferably ~3% by mass, and even more preferably 0.05 to 2.5% by mass.

One type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total amount is preferably 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 for electrodes, wiring, and the like. A silane coupling agent etc. are mentioned as a metal adhesion improving agent.

Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055 are included. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Et represents an ethyl group.

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

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, still more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit, the adhesiveness between the organic film and the metal layer after the curing process is improved, and when it is at most the above upper limit, the heat resistance and mechanical properties of the organic film after the curing process are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.

<Other additives>
The composition of the present invention may optionally contain various additives such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, A filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, etc. can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

[Sensitizer]
The composition of the invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The electronically excited sensitizer comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes electron transfer, energy transfer, heat generation, and the like. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
Examples of sensitizers include sensitizers such as N-phenyldiethanolamine.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.

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

[Chain transfer agent]
The composition of the invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use compounds 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, preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the total solid content of the composition of the present invention. parts is more preferred, and 1 to 5 parts by mass is even more preferred. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total amount is preferably within the above range.

また、界面活性剤は、国際公開第２０１５／１９９２１９号の段落０１５９～０１６５に記載の化合物を用いることもできる。[Surfactant]
Various types of surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various kinds 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 parenthesis indicating the repeating unit of the main chain indicates the content (mol %) of each repeating unit, and the parenthesis indicating the repeating unit of the side chain indicates the repeating number of each repeating unit.

In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

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

[Higher Fatty Acid Derivative]
In the composition of the present invention, in order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added and unevenly distributed on the surface of the composition during the drying process after application. may

Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 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% by 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 thereof may be used. When two or more higher fatty acid derivatives are used, the total amount is preferably within the above range.

<Restrictions on other contained 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 coating surface properties.

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

In addition, as a method for reducing metal impurities unintentionally contained in the composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the composition of the present invention. Examples include a method of performing filter filtration on the raw material to be filtered, and a method of lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.

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, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. More preferred. 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. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.

A conventionally known container can be used as the container for the composition of the present invention. In addition, in order to suppress the contamination of raw materials and compositions with impurities, the storage container is a multi-layer bottle whose inner wall is made of 6 types and 6 layers of resin, and 6 types of resin are used in a 7-layer structure. It is also preferred to use a bottle that has been sealed. Examples of such a container include the container described in JP-A-2015-123351.

<Preparation of composition>
The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and conventionally known methods can be used.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters 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. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When pressurizing and filtering, the pressure to pressurize is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Application of organic film>
The organic film of the present invention is preferably used as an interlayer insulating film for rewiring layers.
In addition, it can also be used for an insulating film of a semiconductor device or a stress buffer film.

(Composition)
The composition of the present invention is a composition used for forming the organic film of the present invention.
Each component contained in the composition of the present invention has the same meaning as each component 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, heating, or the like.

(Organic film, laminate, semiconductor device, and method for producing the same)
Next, organic films, laminates, semiconductor devices, and manufacturing methods thereof will be described.

The organic film of the present invention is preferably a cured product of a coating film of the composition. The film thickness of the organic film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers, or three to seven layers of the organic film of the present invention may be laminated to form a laminate. The laminate of the present invention is preferably a laminate having two or more layers of organic films and a metal layer between the organic films. Moreover, it is preferable that the laminate of the present invention includes two or more layers of 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 of 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. For example, both the first organic film and the second organic film are the composition of the present invention. A preferred embodiment is a film obtained by curing the above. The composition of the present invention used for forming the first organic film and the composition of the present invention used for forming the second organic film may have the same composition, Compositions with different compositions may be used, but from the viewpoint of suitability for production, compositions with the same composition are preferred. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

Fields to which the organic film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above can be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" Published November 2011 , Japan Polyimide/Aromatic Polymer Study Group/Edited "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.

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

The method for producing an organic film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film forming step of applying the composition (the composition of the present invention) to a substrate to form a film. is preferred.
Furthermore, the method for producing an organic film of the present invention includes the film forming step, and further includes an exposure step of exposing the film and a development step of developing the film (developing the film). is more preferable.
Furthermore, the method for producing an organic film of the present invention includes the film forming step (and the developing step, if necessary), and further includes a heating step of heating the film at 50 to 450°C. preferable.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film forming step of applying the composition to a substrate to form a film (composition layer); (b) an exposure step of exposing the film after the film forming step; Developing step (d) of performing development processing 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.

A method for manufacturing a laminate according to a preferred embodiment of the present invention includes the method for manufacturing an organic film of the present invention. In the method for producing a laminate of the present embodiment, after forming an organic film according to the above method for producing an organic film, the step (a), or the steps (a) to (c), or (a ) to (d) are performed. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the organic films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the organic film, between the organic films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d) ) can be performed a plurality of times to obtain a laminate of organic films.

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

The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials 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, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
As the base material, for example, a plate-like base material (substrate) is used.

Moreover, when forming a composition layer on the surface of a resin layer, such as a composition layer, or the surface of a metal layer, a resin layer or a metal layer becomes a base material.

Coating is preferred as a means of applying the composition to the substrate.

Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also 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, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 3 minutes to 7 minutes.

<Exposure process>
The manufacturing method of the present invention may include an exposure step of exposing the film (composition layer). The amount of exposure is not particularly defined as long as the composition can be cured. For example, it is preferable to irradiate 100 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ/cm ² irradiation. is more preferable.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength: 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, and the like. For the composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.

<Development process>
The manufacturing method of the present invention may include a developing step of developing the exposed film (composition layer). By developing, the unexposed portions (non-exposed portions) are removed. The developing method is not particularly limited as long as a desired pattern can be formed.

Development is performed using a developer. If the composition is a negative composition, the developer removes the unexposed portion (unexposed portion) of the composition layer, and if the composition is a positive composition, the exposed portion is removed. Those from which a portion (exposed portion) is removed can be used without particular limitation.
In the present invention, the case where an alkaline developer is used as the developer is called alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is called solvent development.

In alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less with respect to the total mass of the developer. is more preferred, and it is particularly preferred that it does not contain an organic solvent.
The developer in alkaline development is more preferably an aqueous solution having a pH of 9-14.
Alkali compounds contained in the developer in alkali development include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, metasilicate. Potassium acid, ammonia, amines, and the like. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and the like. Among them, alkali compounds containing no metal are preferred, and ammonium compounds are more preferred.
Alkaline compounds may be used alone or in combination of two or more. When two or more alkali compounds are used, the total amount is preferably within the above range.

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

Organic solvents include esters 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. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , keto and aromatic hydrocarbons such as toluene, xylene, anisole, and limonene. , and sulfoxides are preferably dimethyl sulfoxide.

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

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

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

After processing with the developer, rinsing may be carried out.
In the case of solvent development, rinsing is preferably performed using an organic solvent different from the developer.
In the case of alkali development, rinsing is preferably performed using pure water.
Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production 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.
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, and the like can proceed in this step.
Further, when 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 decomposes to generate a base, and the polyimide precursor undergoes a cyclization reaction. progresses.
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, and 150° C. or higher. is particularly preferred, 160° C. or higher is more preferred, and 170° C. or higher is most preferred. 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.

Heating is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature increase rate to 12° C./min or less, it is possible to prevent the formation of the organic film. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, 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 up to the maximum heating temperature is started. For example, when the composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying, for example, a temperature 30 to 200° C. lower than the boiling point of the solvent contained in the composition. It is preferable to gradually raise the temperature from .

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

In particular, when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between layers of organic films. Although the reason for this is not clear, it is believed that this temperature allows the polymerizable groups in the resin between the layers to undergo a cross-linking reaction.

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

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The heating step is preferably carried out in an atmosphere of 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, more preferably 20 ppm (volume ratio) or less.

<Metal layer forming step>
The production 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.

The metal layer is not particularly limited, and existing metal species can be used. Copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified. More preferred.

A method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.

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

<Lamination process>
Preferably, the production method of the present invention further includes a lamination step.

The lamination step means that the surface of the organic film (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step. , in that order. However, only the film forming step (a) may be repeated. Also, (d) the heating step may be performed collectively at the end or in the middle of lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and thereafter the laminated composition layers may be cured at once by heating (d). In addition, after the (c) developing step, (e) a metal layer forming step may be included, and at this time, the heating of (d) may be performed each time, or after stacking a predetermined number of times, (d ) may be heated. Needless to say, the lamination step may further include the drying step, the heating step, and the like as appropriate.

After the lamination step, when the lamination step is further performed, a surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. A plasma treatment is exemplified as the surface activation treatment.

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

For example, the resin layer structure is preferably 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably 3 to 5 layers.

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, (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in this order, or (a) film formation (b) the exposure step, (c) the development step, and (e) the metal layer formation step, and the step (d) is collectively provided at the end or in the middle. By alternately performing the lamination step of laminating the composition layer (resin layer) and the metal layer forming step, the composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses semiconductor devices comprising the organic films or laminates of the present invention. Specific examples of a semiconductor device using the composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the descriptions of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. the contents of which are incorporated herein.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, "parts" and "%" are based on mass unless otherwise specified.

上記（ＰＡ－１）中、Ｃ_３Ｈ_６の記載には、１－メチルエチレン基（下記式（Ｐ１））と２－メチルエチレン基（下記式（Ｐ２））がランダムに含まれる。式（Ｐ１）及び式（Ｐ２）中、＊^１は式（ＰＡ－１）におけるＲ中のアクリロキシ基側の構造と結合し、＊^２は式（ＰＡ－１）におけるＲ中の＊側の構造と結合する。

(Synthesis of polyimide precursor resin PA-1)
20.0 g (64.5 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diglyme while removing water in a dry reactor equipped with a stirrer, condenser and a flat-bottomed joint fitted with an internal thermometer. . 10.1 g (77 mmol) of 2-hydroxyethyl methacrylate, 12.6 g (39 mmol) of Blenmer AP-400 (manufactured by NOF Corporation), 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added. and stirred at a temperature of 60° C. for 18 hours. After cooling the mixture to -20°C, 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 before adding 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, to the resulting clear solution, 11.7 g (58.7 mmol) of 4,4′-diaminodiphenyl ether as diamine dissolved in 100 mL of NMP was added dropwise over 1 hour. Viscosity increased during the diamine addition. 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. The polyimide precursor resin was then 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. The resulting polyimide precursor resin was then dried under reduced pressure at 45° C. for one day. The molecular weights of this polyimide precursor resin PA-1 were 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 a binding site with an oxygen atom to which R binds.

In (PA-1) above, the description of C ₃ H ₆ randomly includes a 1-methylethylene group (formula (P1) below) and a 2-methylethylene group (formula (P2) below). In formula (P1) and formula (P2), * ¹ is bonded to the structure on the acryloxy group side in R in formula (PA-1), and * ² is the structure on the * side in R in formula (PA-1). combine with

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

Details of each component described in Table 1 are as follows.

〔solvent〕
・NMP: N-methylpyrrolidone ・GBL: γ-butyrolactone ・DMSO: dimethyl sulfoxide ・EL: ethyl lactate

[Initiator]
・ OXE01: Irgacure OXE01 (manufactured by BASF)
・784EG: Irgacure 784EG (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)
・ 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 with the following structure)

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

[Migration inhibitor]
・H-1: 1H-tetrazole ・H-2: a compound having the following structure

<Evaluation>
[Small angle neutron scattering (SANS) measurement]
A resin layer was formed by applying the composition prepared in each example and comparative example or the composition for comparison to a silicon wafer by spin coating.
The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer having a uniform thickness of about 15 μm on the silicon wafer. The entire surface of the obtained composition layer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). After the exposure, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, reaching 180° C., and then heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution to separate the organic film from the silicon wafer.
The organic film with a thickness of about 15 μm obtained by the above method was cut into a circular shape with a diameter of 18 mm, which was stacked to a thickness of 100 to 200 μm to obtain a sample for measurement. After measuring the mass and film thickness of the measurement sample, the sample was placed in a J-PARC MLF iMATERIA dedicated sample holder for SANS measurement and sealed.

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

-Measurement condition-
MLF neutron beam power: 500 kW
Measurement q value range: 0.007 to 5 Å ^-1 (small angle detector bank (0.007 to 0.5 Å ^-1 ) and low angle detector bank (0.5 to 5 Å) of J-PARC MLF iMATERIA (BL20) ^-1 ) was used.)
Measurement temperature: room temperature (23°C)
Cumulative time: 12-15 minutes/sample

From the measurement results, the values of I/A and I/B were calculated in each example and comparative example, and are shown in the columns of "I/A" and "I/B" in Table 1, respectively.

[Evaluation of Solvent Resistance]
A resin layer was formed on a silicon wafer having a diameter of 4 inches by spin-coating the composition prepared in each example and comparative example or the comparative composition on the silicon wafer.
The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer having a uniform thickness of about 15 μm on the silicon wafer. The entire surface of the obtained composition layer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). After the exposure, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 180° C., the wafer was heated for 3 hours to obtain a silicon wafer with an organic film formed thereon.
After the heating, the film thickness (film thickness A) of the organic film on the silicon wafer was measured. Thereafter, the silicon wafer with the organic film formed thereon was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and air-dried. After the air-drying, the film thickness (film thickness B) of the organic film on the silicon wafer was measured.
The remaining ratio (%) of the film thickness of the organic film was calculated by the following formula, and the calculated value was described in the column of "solvent resistance (unit: %)" in Table 1.
It can be said that the larger the residual ratio (%) of the film thickness of the organic film, the better the solvent resistance of the obtained organic film.
Remaining ratio (%) of film thickness of organic film=film thickness B/film thickness A×100

[Evaluation of breaking elongation]
A resin layer was formed by applying the composition prepared in each example and comparative example or the composition for comparison to a silicon wafer by spin coating.
The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer having a uniform thickness of about 15 μm on the silicon wafer. The entire surface of the obtained composition layer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). After the exposure, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, reaching 180° C., and then heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution to separate the organic film from the silicon wafer.
The peeled organic film was punched out using a punching machine to prepare a test piece having a width of 3 mm and a length of 30 mm. The longitudinal elongation of the obtained test piece was measured using a tensile tester (Tensilon) under an environment of a crosshead speed of 300 mm / min, 25 ° C., 65% RH (relative humidity), according to JIS-K6251. Measured according to Each measurement was performed 5 times, and the arithmetic average value of the elongation rate (elongation at break) when the test piece was broken in the 5 measurements is described in the column of "elongation at break (unit: %)" in Table 1.
It can be said that the larger the arithmetic mean value, the better the elongation at break of the obtained organic film.

From the above results, it can be seen that the organic film according to the present invention is excellent in solvent resistance.
The comparative composition according to Comparative Example 1 has an I/A of 2.413 and an I/B of 0.419, and satisfies neither formula (1) nor formula (2). It can be seen that the organic film according to Comparative Example 1 is inferior in solvent resistance.

Next, instead of the resin PA-1 of Example 1, three compositions each using a closed-ring polyimide resin, a resin containing a polybenzoxazole precursor, or a closed-ring polybenzoxazole were used. , solvent resistance and elongation at break were evaluated in the same manner as in Example 1. Results equivalent to those of Example 1 were obtained in terms of solvent resistance and elongation at break even when any of the above three compositions was used.

<Example 101>
The composition described in Example 1 was applied by spinning onto the surface of the thin copper layer of the resin substrate having the thin copper layer formed thereon so as to have a film thickness of 20 μm. The composition applied to the resin substrate was dried at 100° C. for 2 minutes, and then exposed using a stepper (NSR1505 i6 manufactured by Nikon). Exposure was carried out through a mask of a square pattern (square pattern of 100 μm in length and width, number of repetitions: 10) at a wavelength of 365 nm and an exposure amount of 400 mJ/cm ² to prepare a square pattern. After exposure, the film was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./min, reaching 180° C., and then heated at this temperature for 3 hours to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

Claims (7)

satisfying at least one formula selected from the group consisting of the following formula (1) and the following formula (2);
A cured product of a coating film of a composition containing at least one resin selected from the group consisting of polyimides, polybenzoxazoles, polyimide precursors, and polybenzoxazole precursors, wherein the polyimide is represented by the following formula (2A): an organic film comprising a repeating unit of
Formula (1): I/A≧2.5
Formula (2): I/B≧0.5
In the above formula (1) or the above formula (2), I is the relative intensity value when the small angle neutron scattering measurement is performed with q in the range of 0.030 Å ⁻¹ to 0.065 Å ⁻¹ for the organic film. is the maximum value, A is the minimum value of the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.200 Å ⁻¹ to 0.300 Å ⁻¹ for the organic film, and B is the above It is the minimum value of the relative intensity value when neutron small angle scattering measurement is performed with q in the range of 0.017 Å ⁻¹ to 0.025 Å ⁻¹ for the organic film, and q is the following formula (Q) in small angle scattering. is a value defined by;
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), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group. 2. The organic film of Claim 1 , wherein the composition comprises a photosensitizer. A composition for forming the organic film according to claim 1 or 2 . A laminate comprising two or more layers of the organic film according to claim 1 or 2 , and comprising a metal layer between any of the organic films. A semiconductor device comprising the organic film according to claim 1 or 2 or the laminate according to claim 4 . 3. A method for producing an organic film according to claim 1, comprising a film forming step of applying the composition to a substrate to form a film. 7. The method for producing an organic film according to claim 6 , comprising heating the film at 50 to 450.degree.