TWI886225B - Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention is a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, wherein the photosensitive resin composition comprises: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; an organic metal complex having photopolymerization initiation ability; and a hindered phenol compound, and when a film composed of the photosensitive resin composition with a film thickness of 15 μm is formed by heating at 100° C. for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6.

Description

Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device

The present invention relates to a photosensitive resin composition, a hardened film, a laminate, a hardened film manufacturing method and a semiconductor device.

Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulation, and are therefore suitable for various uses. The above uses are not particularly limited, but for example, for semiconductor devices for packaging, they can be used as materials for insulating films or sealing materials, or as protective films. In addition, they are also used as base films or coverlay films for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of a photosensitive resin composition containing resins such as polyimide and polybenzoxazole, or containing such precursors. The photosensitive resin composition is applied to a substrate, for example, by coating, to form a photosensitive film, and then exposed, developed, heated, etc. as needed to form a cured product on the substrate. The above-mentioned polyimide precursor and polybenzoxazole precursor are cyclized, for example, by heating, and become polyimide and polybenzoxazole, respectively, in the cured product. The photosensitive resin composition can be applied by a known coating method, and therefore, it can be said that the photosensitive resin composition has a high degree of freedom in designing the shape, size, and application position when applied, and has excellent adaptability in manufacturing. In addition to the high performance of polyimide, polybenzoxazole, etc., from the perspective of excellent adaptability in manufacturing, the application of the above-mentioned photosensitive resin composition in the industry is expected to expand.

For example, Patent Document 1 describes a negative photosensitive resin composition comprising 100 parts by mass of a polyimide precursor of a specific structure, 1 to 20 parts by mass of a photopolymerization initiator, and 0.01 to 10 parts by mass of a monocarboxylic acid compound having 2 to 30 carbon atoms and having one or more functional groups selected from the group consisting of a hydroxyl group, an ether group, and an ester group.

[Patent Document 1] Japanese Patent Application Publication No. 2011-191749

It is required to improve the shape of a pattern when forming a pattern composed of a photosensitive resin composition.

The object of the present invention is to provide a photosensitive resin composition having an excellent pattern shape, a cured film formed by curing the photosensitive resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

Representative embodiments of the present invention are shown below. <1> A photosensitive resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; an organic metal complex having photopolymerization initiation ability; and a hindered phenol compound, wherein a film having a film thickness of 15 μm formed by heating at 100°C for 5 minutes has an absorbance of 0.2 to 0.6 at a wavelength of 405 nm. <2> A photosensitive resin composition, comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; an organic metal complex having a photo-radical polymerization initiation capability; and a hindered phenol compound, for forming a film composed of the photosensitive resin composition, wherein the film thickness of the film is greater than 15 μm, and the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. <3> The photosensitive resin composition as described in <1> or <2>, wherein the organic metal complex has a photo-radical polymerization initiation capability. <4> The photosensitive resin composition as described in any one of <1> to <3>, wherein the metal in the above-mentioned organic metal complex is titanium. <5> The photosensitive resin composition as described in any one of <1> to <4>, wherein the above-mentioned organic metal complex is a metallocene compound. <6> The photosensitive resin composition as described in any one of <1> to <5>, wherein the content of the above-mentioned organic metal complex is 0.5 to 5.0 mass % relative to the total solid content of the photosensitive resin composition. <7> The photosensitive resin composition as described in any one of <1> to <6>, which further contains a sensitizer. <8> A photosensitive resin composition as described in any one of <1> to <7>, wherein the resin is a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, and the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1g of the polyimide precursor is 0.08 to 1.68 mmol/g. <9> A photosensitive resin composition as described in any one of <1> to <8>, which is used to form a photosensitive film for negative type development. <10> A photosensitive resin composition as described in any one of <1> to <9>, which is used to form an interlayer insulating film for a redistribution layer. <11> A cured film formed by curing the photosensitive resin composition described in any one of <1> to <10>. <12> A laminate comprising two or more cured films described in <11>, wherein a metal layer is included between any of the cured films. <13> A method for producing a cured film, comprising: a film forming process, wherein the photosensitive resin composition described in any one of <1> to <10> is applied to a substrate to form a film. <14> The method for producing a cured film as described in <13>, comprising: an exposure process, wherein the film is exposed; and a development process, wherein the film is developed. <15> The method for producing a cured film as described in <13> or <14>, wherein the exposure is performed by a laser direct imaging method. <16> A method for manufacturing a cured film as described in any one of <13> to <15>, which comprises: a heating process of heating the film at 50 to 450°C. <17> A semiconductor device comprising the cured film described in <11> or the laminated body described in <12>. [Effect of the invention]

According to the present invention, there are provided a photosensitive resin composition having an excellent pattern shape, a cured film formed by curing the photosensitive resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

The main embodiments of the present invention are described below. However, the present invention is not limited to the specified embodiments. In this specification, the numerical range represented by the symbol "～" refers to the range including the numerical values recorded before and after "～" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the expected effect of the process can be achieved. In the marking of groups (atomic groups) in this specification, the marking without substitution and unsubstituted includes groups (atomic groups) without substituents, and also includes groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used in exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active light or radiation such as electron beams can be cited. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either "acryl" and "methacryl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and using as columns the protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, the molecular weights are those obtained by measurement using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, the detection in the GPC measurement is those obtained by using a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting the laminate is recorded as "upper" or "lower", it is sufficient that there are other layers on the upper or lower side of the layer that serves as the reference among the multiple layers concerned. That is, a third layer or element may be further inserted between the layer that serves as the reference and the other layers mentioned above, and the layer that serves as the reference and the other layers mentioned above do not need to be in contact. In addition, unless otherwise specified, the direction of stacking layers on the substrate is called "upper", or when there is a photosensitive film, the direction from the substrate toward the photosensitive film is called "upper", and the opposite direction is called "lower". In addition, the setting of the up and down directions is for the convenience of this specification. In actual forms, the "upper" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, in a composition, each component contained in the composition may include two or more compounds corresponding to the component. Also, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, a combination of a preferred embodiment is a more preferred embodiment.

(Photosensitive resin composition) The first aspect of the photosensitive resin composition of the present invention is as follows: a photosensitive resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; an organic metal complex having photopolymerization initiation ability; and a hindered phenol compound, wherein when a film having a film thickness of 15 μm formed by heating at 100°C for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. The second aspect of the photosensitive resin composition of the present invention is as follows: a photosensitive resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; an organic metal complex having a photo-radical polymerization initiation capability; and a hindered phenol compound for forming a film composed of the above-mentioned photosensitive resin composition, wherein the film thickness of the above-mentioned film is 15 μm or more, and the absorbance of the above-mentioned film at a wavelength of 405 nm is 0.2 to 0.6. In the following, when simply described as "photosensitive resin composition", "photosensitive resin composition of the present invention", etc., it refers to both the above-mentioned first aspect and the above-mentioned second aspect. In particular, when only the photosensitive resin composition of the first aspect (second aspect) is described, it is described as "the photosensitive resin composition of the first aspect", "the photosensitive resin composition of the second aspect", etc.

The photosensitive resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent. In addition, the photosensitive resin composition of the present invention is preferably used to form a photosensitive film for negative development. In the present invention, negative development refers to development in which the non-exposed part is removed by development during exposure and development, and positive development refers to development in which the exposed part is removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method described in the exposure process in the description of the method for producing a cured film described later, the developer and the development method described in the development process can be used.

The photosensitive resin composition of the present invention has excellent exposure sensitivity and pattern shape of the obtained pattern. Although the mechanism by which the above effect can be obtained is unclear, it can be inferred as follows.

For example, as described in Patent Document 1, an organic titanium compound having polymerization initiation energy is added to a photosensitive resin composition. However, when a photosensitive film is formed from a photosensitive resin composition containing an organic metal complex and exposed and developed, a pattern with excellent pattern shape may not be obtained. In the present invention, the excellent shape of the pattern means that the angle (taper angle) formed by the surface of the substrate on which the pattern is formed and the side of the pattern is close to the desired angle, and the cross-sectional shape of the pattern is not a constricted shape. As a result of in-depth research by the inventors, it was found that by using a photosensitive resin composition containing an organic metal complex and a hindered phenol compound, and forming a film composed of the above-mentioned photosensitive resin composition with a film thickness of 15μm by heating at 100°C for 5 minutes (also referred to as a "specific film"), the absorbance of the above-mentioned film at a wavelength of 405nm is 0.2 to 0.6, or a photosensitive resin composition containing an organic metal complex and a hindered phenol compound, and providing a film composed of the above-mentioned photosensitive resin composition, the film thickness of the above-mentioned film is 15μm or more, and the absorbance of the above-mentioned film at a wavelength of 405nm is 0.2 to 0.6, even when a thick film (for example, 15μm or more) is formed, the pattern shape is excellent. Although the mechanism for achieving the above effect is not clear, it can be inferred as follows. Since the absorbance of the specific film or the film composed of the photosensitive resin composition at a wavelength of 405nm is 0.2 to 0.6, it is believed that the exposure light can easily penetrate deep into the pattern, and the pattern shape is excellent. In addition, since the volatility of the hindered phenol compound is low, it is believed that even in the position of the exposure light side of the pattern, it is possible to suppress unnecessary polymerization reaction, and the pattern shape is excellent. In addition, for example, when a photosensitive film is formed by contacting a metal layer, and the photosensitive resin composition includes at least one resin selected from a group including a polyimide precursor or a polybenzoxazole precursor, the hindered phenol compound is easily distributed unevenly on the surface of the metal layer, and the crosslinking density in the deep part of the film is easily within an appropriate range. Therefore, it is believed that the above-mentioned precursor is easily cyclized after the pattern is formed, and a cured film with excellent adhesion, mechanical properties and chemical resistance is easily obtained. The photosensitive resin composition of the present invention is described in detail below.

<Absorbance> [First Aspect] Regarding the photosensitive resin composition of the first aspect of the present invention, when a film composed of the photosensitive resin composition having a film thickness of 15 μm is formed by heating at 100°C for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6. The heating is not particularly limited, and can be performed, for example, by the method described in the embodiments described below. The absorbance of the film having a film thickness of 15 μm at a wavelength of 405 nm is preferably 0.2 to 0.5, and more preferably 0.2 to 0.4. Furthermore, regarding the photosensitive resin composition of the first embodiment, the absorbance at a wavelength of 405 nm of a film having a thickness of 20 μm formed by the same method is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and further preferably 0.2 to 0.4. Furthermore, regarding the photosensitive resin composition of the first embodiment, the absorbance at a wavelength of 405 nm of a film having a thickness of 30 μm formed by the same method is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and further preferably 0.2 to 0.4. The above absorbance is not particularly limited, and can be measured, for example, using an ultraviolet-visible spectrophotometer. The above absorbance can be adjusted, for example, by the structure of the specific resin contained in the photosensitive resin composition (for example, the structure of the monomer used in the specific resin, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor, the content of the benzoxazole structure in the polybenzoxazole precursor, etc.), the type and content of the compound having absorption at a wavelength of 405 nm, etc.

[Second Aspect] The photosensitive resin composition of the second aspect of the present invention is used to form a film composed of the above-mentioned photosensitive resin composition, the film thickness of the above-mentioned film is 15μm or more, and the absorbance of the above-mentioned film at a wavelength of 405nm is 0.1 to 0.6. The method for forming the above-mentioned film is not particularly limited, and for example, the film forming method described in the film forming process described later can be cited. The film composed of the above-mentioned photosensitive resin composition is preferably a dry film formed by drying the above-mentioned photosensitive resin composition. The film thickness of the above-mentioned film can be set to 20μm or more, and can also be set to 30μm or more. The upper limit is not particularly limited, for example, it can be set to 50μm or less. The absorbance of the above film at a wavelength of 405 nm is preferably 0.2 to 0.5, and more preferably 0.2 to 0.4. The above absorbance is not particularly limited, and can be measured, for example, using an ultraviolet-visible spectrophotometer. The above absorbance can be adjusted, for example, by the structure of the specific resin contained in the photosensitive resin composition (for example, the structure of the monomer used in the specific resin, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor, the content of the benzoxazole structure in the polybenzoxazole precursor, etc.), the type and content of the compound having absorption at a wavelength of 405 nm, etc.

<Specific resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole. In the photosensitive resin composition of the present invention, it is preferred to contain polyimide or polyimide precursor as the specific resin, and it is more preferred to contain polyimide precursor. Furthermore, from the viewpoint of easily obtaining the above-mentioned cured film having excellent adhesion, mechanical properties or chemical resistance, the photosensitive resin composition of the present invention preferably contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, and more preferably contains a polyimide precursor. Furthermore, it is preferred that the specific resin has a free radical polymerizable group. When the specific resin has a free radical polymerizable group, the photosensitive resin composition preferably includes the photo free radical polymerization initiator described below as a photosensitizer, more preferably includes the photo free radical polymerization initiator described below as a photosensitizer and includes the free radical crosslinking agent described below, and further preferably includes the photo free radical polymerization initiator described below as a photosensitizer, includes the free radical crosslinking agent described below, and includes the sensitizer described below. For example, a negative photosensitive film is formed from the photosensitive resin composition.

[Polyimide precursor] The polyimide precursor used in the present invention is a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure. The total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the above polyimide precursor is preferably 0.08 to 1.68 mmol/g, more preferably 0.10 to 1.00 mmol/g, further preferably 0.12 to 0.80 mmol/g, and particularly preferably 0.15 to 0.60 mmol/g. Furthermore, the polyimide precursor used in the present invention is preferably a polyimide precursor containing a cyclic imide structure. Furthermore, after the polyimide precursor of the present invention is dissolved in a solvent and applied to a substrate, the absorbance of a film with a thickness of 15 μm obtained by removing (drying) the solvent is preferably 0.2 to 0.6, and more preferably 0.2 to 0.5. The polyimide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but preferably has it in the main chain. In this specification, "main chain" refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" refers to other bond chains.

The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferably a polyimide precursor comprising a repeating unit represented by the following formula (2). [Chemical Formula 1] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups. Groups composed of linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 6 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms or combinations thereof are preferred, and groups containing aromatic groups having 6 to 20 carbon atoms are more preferred. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, and L is a group consisting of an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more thereof. The preferred ranges are as described above.

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

[Chemical formula 2] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine can be cited; 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’-diaminodiphenyl sulfide, 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) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy) biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide, Bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2 -Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4- and 2,5-diaminoisopropylbenzene, 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, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1, 5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) Biphenyl, 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfonium, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotolidine and 4,4’-diaminotetraphenyl.

Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred.

Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

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

Furthermore, from the viewpoint of the i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of the i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 3] In formula (51), R ⁵⁰ to R ⁵⁷ are 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 trifluoromethyl group. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 4] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds that provide 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, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical Formula 5]

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with other structures. [Chemical Formula 6] In formula (5), R ¹¹² is preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ -.

Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 7] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-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 C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, examples of R ¹¹¹ include a residual group of a diaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxadiazole group, a blocked isocyanate group, a hydroxymethyl group, and an amine group. As the free radical polymerizable group possessed by a polyimide precursor, a group having an ethylenic unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[Chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a polyalkylene group. Preferred examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group. An ethylene group, a propylene group, a trimethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group are more preferred, and a polyalkylene group is further preferred. In the present invention, a polyalkoxyl group refers to a group directly bonded with two or more alkoxyl groups. The alkylene groups in the plural alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains plural alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. In addition, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups is preferred, polyethoxy or polypropoxy is more preferred, and polyethoxy is further preferred. In the group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy groups and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of the ethoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, there can be mentioned an aromatic group and an aralkyl group having an acidic group bonded to one, two or three carbon atoms, preferably one carbon atom, constituting the aromatic group. Specifically, there can be mentioned an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, there can be mentioned a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. It is also more preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group.

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 to 30. The alkyl group may be any of a linear, branched, or cyclic group. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic or polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of both high sensitivity and stability. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group may be specifically a substituted or unsubstituted benzene ring, a naphthyl ring, a pentadiene ring, an indene ring, an azulene ring, a heptadiene ring, an indenyl ring, a perylene ring, a condensed pentadiene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed benzene ring, a chrysene ring, a tert-butylbenzene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ring, The ring may be a pyridine ring, a pyrimidine ring, a pyrimidine ring, an indole ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a pyridine ring, a naphthidine ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthidine ring, an acridine ring, a phenanthroline ring, a thianthiophene ring, a chromene ring, a pyridine ring, a phenanthroline ring, a phenanthiophene ring, a phenanthiophene ring or a phenanthiophene ring. The benzene ring is the most preferred.

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

In addition, the polyimide precursor preferably has fluorine atoms in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10 mass % or more, and preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, there can be cited an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the width of the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 9] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are polymerizable groups.

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

The polyimide precursor may contain one or more types of the repeating unit represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating unit represented by formula (2). Furthermore, the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by formula (2).

The polyimide precursor may contain at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-6) as a repeating unit having a cyclic imide structure or a cyclic isoimide structure. [Chemical Formula 10] In formula (2-1) to formula (2-6), R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ , and A ² have the same meanings as R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ , and A ² in the above formula (2), respectively, and preferred embodiments are also the same.

The total content of the repeating units represented by any one of Formulae (2-1) to (2-6) is preferably within the above range as the total molar amount of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor.

As an embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content, except that all the repeating units in the terminal polyimide precursor can be any of the repeating units represented by formula (2) and any of the repeating units represented by formulas (2-1) to (2-6).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is still further preferred, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is a value calculated using 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 having an organic solvent as a main component. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more relative to 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of the polyimide, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulation of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

-Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has fluorine atoms. The fluorine atoms are preferably contained in R ¹³² in the repeating unit represented by the formula (4) described below or R ^{131 in the repeating unit represented by the formula (4) described below, and are more preferably contained in R 132} in the repeating unit represented by the formula (4) described below or R ¹³¹ in the repeating unit represented by the formula (4) described below as a fluorinated alkyl ^group . The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1 to 50 mol/g, and more preferably 5 to 30 mol/g.

-Silicon Atoms- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has silicon atoms. The silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, and is more preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later as an organic modified (poly)siloxane structure described later. In addition, the above silicon atom or the above organic modified (poly)siloxane structure may also 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 the polyimide is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g.

- Ethylenically unsaturated bonds - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. The polyimide may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that the ethylenically unsaturated bonds are in the side chains. It is preferable that the above-mentioned ethylenically unsaturated bonds have free radical polymerizability. It is preferred that the ethylenic unsaturated bond is contained in ^R132 in the repeating unit represented by the formula (4) described later or in ^R131 in the repeating unit represented by the formula (4) described later, and it is more preferred that the ethylenic unsaturated bond is contained in ^R132 in the repeating unit represented by the formula (4) described later or in ^R131 in the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond. Among them, it is preferred that the ethylenic unsaturated bond is contained in ^R131 in the repeating unit represented by the formula (4) described later, and it is more preferred that the ethylenic unsaturated bond is contained in ^R131 in the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond. Examples of the group having an ethylenic unsaturated bond include a group directly bonded to an aromatic ring and having a vinyl group which may be substituted, such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[Chemical formula 11]

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

In formula (IV), ^R21 represents an alkylene group having 2 to 12 carbon atoms, -O- _CH2CH (OH) _CH2- , -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of carbon atoms repeated is preferably 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group consisting of two or more of the above groups in combination.

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 12] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of them, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (for example, 2-isocyanateethyl methacrylate). The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (e.g., glycidyl methacrylate, etc.). As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups is preferred, polyethoxy or polypropoxy is more preferred, and polyethoxy is further preferred. In the group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. Preferred aspects of the repetition numbers of the ethoxy groups and the like in these groups are as described above.

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

The amount of ethylenic unsaturated bonds relative to the total mass of polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g. In addition, from the perspective of production suitability, the amount of ethylenic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

- Crosslinking groups other than ethylenic unsaturated bonds - Polyimide may have crosslinking groups other than ethylenic unsaturated bonds. Examples of crosslinking groups other than ethylenic unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutylene groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. Crosslinking groups other than ethylenic unsaturated bonds are preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later. The amount of crosslinking groups other than ethylenic unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g. Furthermore, from the viewpoint of production suitability, the amount of crosslinking groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.

-Acid value- When polyimide is subjected to alkaline development, the acid value of the 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 the developability. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and more preferably 200 mgKOH/g or less. In addition, when polyimide is subjected to development using a developer containing an organic solvent as the main component, the acid value of the polyimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and more preferably 5 to 20 mgKOH/g. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. In addition, as the acid group contained in the polyimide, from the viewpoint of both storage stability and developing property, the acid group with a pKa of 0 to 10 is preferred, and the acid group with a pKa of 3 to 8 is more preferred. pKa is a dissociation reaction in which hydrogen ions are released from an acid and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this specification, pKa is a calculated value based on ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, the values described in "Revised 5th Edition Chemical Handbook Basic Edition" compiled by the Chemical Society of Japan can also be referred to. Furthermore, when the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group including a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

- Phenolic hydroxyl group - From the viewpoint of making the developing speed based on the alkaline developer appropriate, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is preferably contained in R ¹³² in the repeating unit represented by the formula (4) described later or in R ¹³¹ in the repeating unit represented by the formula (4) described later. The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and has a polymerizable group. Formula (4) [Chemical Formula 13] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When there is a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide. Formula (4-1) [Chemical Formula 14] In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [Chemical formula 15] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group. If not a polymerizable group, it is an organic group. The other groups have the same meanings as those in formula (4).

The polymerizable group is synonymous with the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor. R ¹³¹ represents a divalent organic group. As the divalent organic group, the same as R ¹¹¹ in formula (2) can be exemplified, and the preferred range is also the same. In addition, as R ¹³¹ , a diamine residue remaining after removing the amino group of a diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, the example of R ¹¹¹ in formula (2) of the polyimide precursor can be cited.

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

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

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

^R132 may be a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. As a specific example, ^R115 in the formula (2) of the polyimide precursor may be cited. From the viewpoint of the strength of the organic film, ^R132 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, as R ¹³¹ , preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18), and as R ¹³² , more preferred examples include the above-mentioned (DAA-1) to (DAA-5).

Furthermore, the polyimide preferably has fluorine atoms in the structural unit. The content of fluorine atoms in the polyimide is preferably 10 mass % or more, and more preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

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

-Imidization rate (ring closure rate)- From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. There is no particular upper limit to the above-mentioned imidization rate, as long as it is 100% or less. The above-mentioned imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ^-1 , which is an absorption peak originating from the imide structure. Then, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ^-1 . The imidization rate of the polyimide can be calculated using the peak intensities P1 and P2 obtained from the following formula: Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

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

Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with a diamine compound (a portion of which is replaced by a monoamine end-capping agent) at low temperature; a method of reacting tetracarboxylic dianhydride (a portion of which is replaced by an acid anhydride or a monoacyl chloride compound or a monoactive ester compound end-capping agent) with a diamine compound at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester with a diamine (a portion of which is replaced by a monoamine end-capping agent) in the presence of a condensation agent; A method of obtaining a polyimide precursor by a method such as obtaining a diester from tetracarboxylic dianhydride and an alcohol, then acylation of the remaining dicarboxylic acid, and reacting the resulting product with a diamine (part of which is replaced with a monoamine end-capping agent), and completely imidizing the product using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer with the polyimide precursor. Commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN).

The weight average molecular weight (Mw) of the polyimide can be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 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 with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when containing two or more polyimides, it is preferred that the weight average molecular weight of at least one polyimide is within the above range.

[Polybenzoxazole precursor] Regarding the polybenzoxazole precursor used in the present invention, the molar content of the benzoxazole structure in 1 g of the polybenzoxazole precursor is preferably 0.22 to 3.97 mmol/g, more preferably 0.25 to 3.00 mmol/g, further preferably 0.28 to 2.50 mmol/g, and particularly preferably 0.30 to 2.00 mmol/g.

The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably comprises a repeating unit represented by the following formula (3). [Chemical Formula 16] In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ are synonymous with R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, it is preferred that at least one of them is 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 straight-chain aliphatic group is preferred. It is preferred that R ¹²¹ is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more dicarboxylic acid residues may be used.

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred. As the dicarboxylic acid containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred, and dicarboxylic acids composed of linear or branched (preferably linear) aliphatic groups and 2 -COOH groups are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. As dicarboxylic acids containing a linear aliphatic group, there can be mentioned 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-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

[Chemical formula 17] (In the formula, Z is a carbonyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

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

[Chemical formula 18] In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * represents a bonding site with other structures independently.

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

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2), and the preferred range is also the same. The group ¹²² is preferably derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-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, etc. Such bisaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, the following diaminophenol derivatives having an aromatic group are preferred.

[Chemical formula 19] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, and * and # represent the bonding site with other structures. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. In addition, ^R122 is also preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is preferred that the two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or the two * are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that the two * are bonding sites to the oxygen atom to which R 122 in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded, and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

[Chemical formula 20]

In formula (As), _R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[Chemical formula 21] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is particularly preferred to have a substituent at _R3 adjacent to the phenolic hydroxyl group because the carbonyl carbon of the amide bond and the hydroxyl group are closer together, thereby further improving the effect of achieving a high cyclization rate during curing at a low temperature.

In the above formula (As), when R ₂ and R ₃ are both alkyl groups, it is preferred because high transparency to I-rays and high cyclization rate during curing at low temperatures can be maintained.

In the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group as _R1 include a linear or branched alkyl group having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, and -C(CH3 _)2- are more _preferred from the viewpoint of obtaining _a polybenzoxazole precursor having an excellent balance of maintaining high transparency to I-rays and high cyclization rate _when curing at low temperature and having sufficient solubility in solvents.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), reference may be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 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, and the contents thereof are incorporated into the present specification. However, the present invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of the above formula (3). As the repeating units having a benzoxazole structure, the polybenzoxazole precursor may contain at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and a repeating unit represented by the following formula (3-3). [Chemical Formula 22] In formula (3-1) to formula (3-3), R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ have the same meanings as R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in formula (3), respectively, and preferred embodiments are also the same.

The content of the repeating unit represented by the formula (3-1), the repeating unit represented by the formula (3-2), and the repeating unit represented by the formula (3-3) is preferably such that the molar amount of the benzoxazole structure in 1 g of the polybenzoxazole precursor is within the above range.

Furthermore, from the viewpoint of being able to suppress the occurrence of warp associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[Chemical formula 23] In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl 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. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the molar % of the Z portion, structure a is 5 to 95 molar %, structure b is 95 to 5 molar %, and a+b is 100 molar %.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and the effect of suppressing warp and the effect of improving solvent solubility can be taken into account.

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

For example, when the polybenzoxazole precursor is used in the composition described below, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the above polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and even more preferably 2.2 or less.

[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. [Chemical Formula 24] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polymerizable group, the polymerizable group may be located on at least one of R ¹³³ and R ¹³⁴ , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [Chemical Formula 25] 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 the same as those in formula (X). Formula (X-2) [Chemical Formula 26] In formula (X-2), R ¹³⁷ is a polymerizable group, and the others are substituents. The other groups have the same meanings as in formula (X).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor and the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include aliphatic and aromatic groups. As a specific example, R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be cited. Preferred examples are the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, R ¹²² in the formula (3) of the polybenzoxazole precursor can be cited as an example. Moreover, its preferred example is the same as R ^122. For example, the four bonders of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical Formula 27]

The oxadiazole rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. When the oxadiazole rate is 85% or more, the film shrinkage caused by ring closure generated during oxadiazole by heating is reduced, and the warp can be more effectively suppressed.

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

Polybenzoxazoles are obtained by, for example, reacting a diaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives thereof to obtain a polybenzoxazole precursor, and then oxazolidinizing the precursor by a known oxazolidinization reaction method. In the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives obtained by preliminarily reacting 1-hydroxy-1,2,3-benzotriazole or the like can be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By 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 with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[Production method of polyimide precursor, etc.] Polyimide precursor, etc. is obtained by reacting dicarboxylic acid or dicarboxylic acid derivative with diamine. It is preferably obtained by halogenating dicarboxylic acid or dicarboxylic acid derivative with diamine using a halogenating agent. In the production method of polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one or two or more. As the organic solvent, it can be appropriately specified according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone and N-ethylpyrrolidone. Polyimide can be produced by cyclizing a polyimide precursor by thermal imidization, chemical imidization (for example, by promoting a cyclization reaction by the action of a catalyst), or the like, or directly synthesizing the polyimide.

Furthermore, it is also preferable to use a non-halogen catalyst for synthesis instead of the above-mentioned halogenating agent. As the above-mentioned non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, for example, boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, and carbodiimide compounds can be mentioned. As the above-mentioned carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. can be mentioned.

-Capping agent- When manufacturing polyimide precursors, it is preferred to seal the ends of the polyimide precursors with a capping agent such as an acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound in order to further improve storage stability. As the end-capping agent, it is more preferable to use a monoamine. As preferred compounds of the monoamine, there can be cited aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation- When manufacturing a polyimide precursor, etc., a process for solid precipitation may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, thereby enabling solid precipitation. Then, the polyimide precursor is dried to obtain a powdered polyimide precursor.

[Content] The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, and 50% by mass or more relative to the total solid content of the composition. In addition, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, 99% by mass or less is more preferably, 98% by mass or less is more preferably, 97% by mass or less is more preferably, and 95% by mass or less is more preferably relative to the total solid content of the composition. The composition of the present invention may contain only one specific resin or two or more. When containing two or more, it is preferred that the total amount be within the above range.

Furthermore, the photosensitive resin composition of the present invention preferably contains at least two resins. Specifically, the photosensitive resin composition of the present invention may contain two or more specific resins and other resins described below in total, or may contain two or more specific resins, but containing two or more specific resins is preferred. When the photosensitive resin composition of the present invention contains two or more specific resins, for example, it is preferred that the photosensitive resin composition contains two or more polyimide precursors having different structures derived from dianhydrides (R ¹¹⁵ described in the above formula (2)).

<Organometallic complex with photopolymerization initiation ability> The photosensitive resin composition of the present invention contains an organic metal complex with photopolymerization initiation ability (hereinafter, also referred to as "specific organic metal complex"). In the present invention, having photopolymerization initiation ability means that polymerization initiation species capable of initiating polymerization can be generated by irradiation with light. For example, when a composition containing a crosslinking agent and an organic metal complex is irradiated with light in a wavelength region where the organic metal complex absorbs light and the crosslinking agent does not absorb light, the presence or absence of photopolymerization initiation ability can be confirmed by confirming the disappearance of the crosslinking agent. When confirming the disappearance, an appropriate method can be selected according to the type of the crosslinking agent, for example, IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) can be used for confirmation.

It is preferred that the specific organometallic complex has the ability to initiate photoradical polymerization. In the present invention, the ability to initiate photoradical polymerization means that free radicals capable of initiating free radical polymerization can be generated by irradiation with light. For example, when a composition comprising a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of the ability to initiate photoradical polymerization can be confirmed by confirming the disappearance of the free radical crosslinking agent. When confirming the disappearance, an appropriate method can be selected according to the type of the free radical crosslinking agent, such as by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography).

The metal contained in the specific organometallic complex is not particularly limited, but is preferably a transition metal, preferably a metal corresponding to the Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium and einsteinium, further preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

Regarding the specific organometallic complex, a compound in which an organic group is coordinated with a metal atom is preferred, and a metallocene compound is more preferred. In the present invention, a metallocene compound refers to an organometallic complex having two cyclopentadienyl derivatives which may have substituents as η5-ligands. As the above-mentioned organic group, there is no particular limitation, and a group consisting of a alkyl group or a combination of a alkyl group and a heteroatom is preferred. As a heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferred. In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and it is more preferred that at least two of them are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and a 5-membered cyclic group is more preferably. The cyclic group may be a cyclic group or a heterocyclic group, but a cyclic group is preferably a cyclic group. As the 5-membered cyclic group, a cyclopentadienyl group is preferably used. In addition, the specific organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

Among them, as the specific organometallic complex, a titanocene compound is preferred, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium or bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium is more preferred.

The content of the specific organic metal complex is preferably 0.1 to 20 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is 0.2 mass % or more, more preferably 0.5 mass % or more, and particularly preferably 1.0 mass % or more. The upper limit is 10 mass % or less, more preferably 5.0 mass % or less. The specific organic metal complex can be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

<Hindered phenol compound> The photosensitive resin composition of the present invention contains a hindered phenol compound. The hindered phenol compound is not particularly limited, but is preferably a compound represented by the following formula (1-1) or a compound containing the structure represented by the formula (1-1) as a partial structure, and more preferably a compound containing the structure represented by the formula (1-1) as a partial structure. [Chemical Formula 28]

In formula (1-1), Ar represents an aromatic ring structure, a represents an integer greater than or equal to 1, ^R1 represents a branched alkyl group, b represents an integer greater than or equal to 1, ^R2 represents a substituent, and c represents an integer greater than or equal to 1.

In formula (1-1), Ar represents an aromatic ring structure, preferably an aromatic hydrocarbon ring structure, and more preferably a benzene ring structure. a represents an integer greater than 1, preferably an integer from 1 to 3, more preferably 1 or 2, and more preferably 1. ^R1 represents a branched alkyl group, preferably a branched alkyl group containing at least 1 quaternary carbon atom, more preferably a branched alkyl group containing 1 quaternary carbon atom, and more preferably tert-butyl. b represents an integer greater than 1, preferably an integer from 1 to 3, more preferably 1 or 2, and more preferably 1. ^R2 represents a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. When the hindered phenol compound is a compound containing the structure represented by formula (1-1) as a partial structure, a compound having one hydrogen atom directly bonded to a ring member of the aromatic ring structure represented by Ar in formula (1-1) removed is preferred.

It is preferred that at least one of the hydroxyl groups described in formula (1-1) and at least one of R ¹ exist at adjacent positions in the aromatic ring structure represented by Ar. In the present specification, two groups exist at adjacent positions in the ring structure, which means that the ring member in the ring structure of a certain group and the ring member in the ring structure of another group are adjacent ring members in the ring structure. For example, when the ring structure is a benzene ring structure, the adjacent positions are adjacent positions.

In addition, the hindered phenol compound is preferably a compound containing a nitrogen atom. Since the hindered phenol compound contains a nitrogen atom, it is considered that the hindered phenol compound is easily distributed unevenly on the surface of the metal layer, and the crosslinking density in the deep part of the film is easily within an appropriate range. In particular, the hindered phenol compound contains a nitrogen atom, and the embodiment in which the specific resin contains a polyimide precursor and a polybenzoxazole precursor is one of the preferred embodiments of the present invention. When the hindered phenol compound is a compound containing a nitrogen atom, the hindered phenol compound is preferably a compound containing a nitrogen-containing ring structure such as a tris ring structure, a toluidine ring structure or an aliphatic ring structure such as an isocyanuric acid ring structure, and is more preferably a compound containing a nitrogen-containing aliphatic ring structure such as an isocyanuric acid ring structure. When the hindered phenol compound contains a nitrogen-containing ring structure, the hindered phenol compound is preferably a compound having one hydrogen atom directly bonded to the nitrogen-containing ring structure and the aromatic ring structure represented by Ar in the above formula (1-1) removed.

As hindered phenol compounds, compounds represented by the following formulas (1-1-1) to (1-1-7) can be cited, but are not limited thereto. Among them, the compound represented by formula (1-1-1) is preferred. [Chemical Formula 29]

The content of the hindered phenol compound relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.05 to 10 mass %. The lower limit is preferably 0.1 mass %, more preferably 0.2 mass %, and particularly preferably 0.3 mass %. The upper limit is preferably 5 mass %, and more preferably 3 mass %. The hindered phenol compound can be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

<Other organic metal compounds> The photosensitive resin composition of the present invention may also contain other organic metal compounds (hereinafter, also referred to as "organic metal compounds") different from the above-mentioned specific organic metal complex. It is preferred that other organic metal compounds do not have the ability to initiate free radical polymerization. The organic metal compound may be any organic compound containing a metal atom, but a compound containing a metal atom and an organic group is preferred, a compound in which the organic group is coordinated with the metal atom is more preferred, and a metallocene compound is further preferred. In the present invention, a metallocene compound refers to an organic metal compound having two cyclopentadienyl derivatives which may have substituents as η5-ligands. As the above-mentioned organic group, there is no particular limitation, and a group consisting of a alkyl group or a combination of an alkyl group and a heteroatom is preferred. As heteroatoms, oxygen atoms, sulfur atoms, and nitrogen atoms are preferred. In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and it is more preferred that at least two of them are cyclic groups. The cyclic group is preferably selected from a cyclic group with five members and a cyclic group with six members, and it is more preferred that the cyclic group is a cyclic group with five members. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As a cyclic group with five members, a cyclopentadienyl group is preferred. In addition, the organometallic compound used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic compound is not particularly limited, but is preferably a metal corresponding to the Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium and einsteinium, further preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

The organometallic compound may contain two or more metal atoms, or may contain only one metal atom, but it is preferred to contain only one metal atom. When the organometallic compound contains two or more metal atoms, it may contain only one metal atom, or may contain two or more metal atoms.

The organic metal compound is preferably a titanocene compound, a zirconocene compound or a bezocenocene compound, a titanocene compound or a zirconocene compound is more preferred, and a titanocene compound is further preferred. The organic metal compound is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxy titanium compounds, titanium acylate compounds, chelated titanium compounds, zirconocene compounds and bezocenocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and bezocenocene compounds, further preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

The molecular weight of the organometallic compound is preferably 50 to 2,000, more preferably 100 to 1,000.

As the organometallic compound, a compound represented by the following formula (P) can be preferably cited. [Chemical Formula 30] In formula (P), M is a metal atom, and R is independently a substituent. Preferably, the R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

In formula (P), the metal atom represented by M is preferably a titanium atom, a zirconium atom or an einsteinium atom, more preferably a titanium atom or a zirconium atom, and more preferably a titanium atom. As the aromatic group in R in formula (P), an aromatic group having 6 to 20 carbon atoms can be cited, and an aromatic alkyl group having 6 to 20 carbon atoms is preferred, and phenyl, 1-naphthyl, or 2-naphthyl can be cited. As the alkyl group in R in formula (P), an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and methyl, ethyl, propyl, octyl, isopropyl, t-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be cited. As the halogen atom in the above R, F, Cl, Br, and I can be cited. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and methyl, ethyl, propyl, octyl, isopropyl, t-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be cited. The above R may also have a substituent. As examples of the substituent, halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino can be cited.

Specific examples of the organometallic compound are not particularly limited, but include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetylacetate)titanium, diisopropoxybis(acetylacetone)titanium, pentamethylcyclopentadienyltrimethoxide titanium, and the following compounds. [Chemical Formula 31]

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organic metal compound relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 30 mass %. The lower limit is 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is 25 mass % or less, more preferably. One or more organic metal compounds can be used. When two or more are used, the total amount is preferably within the above range.

<Other resins> The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins"). As other resins, polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding a highly polymerizable acrylic resin having a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the crosslinking agent described below, the coating properties of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the composition is preferably 0.01 mass% or more, 0.05 mass% or more is more preferably, 1 mass% or more is further preferably, 2 mass% or more is further preferably, 5 mass% or more is further preferably, and 10 mass% or more is further preferably. In addition, the content of the other resins in the composition of the present invention relative to the total solid content of the composition is preferably 80 mass% or less, 75 mass% or less is more preferably, 70 mass% or less is further preferably, 60 mass% or less is further preferably, and 50 mass% or less is further preferably. In addition, as a preferred embodiment of the composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above 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 other resin, or may contain two or more. When containing two or more, it is preferred that the total amount be within the above range.

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

As esters, preferred examples include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3- ethyl ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

As ethers, preferred ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea 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, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate and the like.

As ketones, preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.

Preferred examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfoxides, dimethyl sulfoxide is preferably mentioned.

As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As the urea, preferably, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like can be cited.

As alcohols, there can be cited methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl phenyl carbinol, n-pentanol, methyl pentanol and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, it is also preferred that the solvent is in the form of a mixture of two or more solvents.

In the present invention, a solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of the above solvents is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone is also preferred.

From the viewpoint of coating properties, the content of the solvent is preferably 5 to 80 mass % of the total solid content of the photosensitive resin composition of the present invention, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 40 to 70 mass %. The content of the solvent can be adjusted according to the required thickness of the coating and the coating method.

The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount of the solvents is within the above range.

<Photosensitive agent> It is preferred that the composition of the present invention contains a photosensitive agent. It is assumed that the photosensitive agent does not contain a compound corresponding to the above-mentioned specific organic metal complex. The composition of the present invention may contain a photopolymerization initiator different from the above-mentioned specific organic metal complex.

[Photopolymerization initiator] In the composition of the present invention, a photopolymerization initiator may be included as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer in some way.

It is also preferred that the composition of the present invention substantially does not contain photopolymerization initiators other than the specific organic metal complex. Substantially not containing photopolymerization initiators other than the above-mentioned specific organic metal complex means that in the composition of the present invention, the content of photopolymerization initiators other than the above-mentioned specific organic metal complex is 5 mass % or less, preferably 3 mass % or less, more preferably 1 mass % or less, and even more preferably 0.1 mass % relative to the total mass of the above-mentioned specific organic metal complex. In addition, it is also preferred that the composition of the present invention contains the above-mentioned specific organic metal complex and a photoradical polymerization initiator. According to this aspect, the exposure sensitivity can be improved. When the composition of the present invention contains a specific organic metal complex and a photo-radical polymerization initiator, the content of the specific organic metal complex relative to the total content of the specific organic metal complex and the photo-radical polymerization initiator is preferably 20 to 80 mass %, and more preferably 30 to 70 mass %. In addition, as the above-mentioned photo-radical polymerization initiator, the oxime compound described later is preferred.

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

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

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

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

As the hydroxyacetophenone-based 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 such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Publication No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

As a photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures or 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 32]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 33]

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 2013-164471.

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzyl-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

Further preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds is further preferred. Using metallocene compounds or oxime compounds is further preferred, and oxime compounds are still further preferred.

In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michelle's ketone) and the like, aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propanone-1, quinones with aromatic ring condensation such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin and benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. In addition, the compound represented by the following formula (I) may be used.

[Chemical formula 34]

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

[Chemical formula 35]

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

Furthermore, the photoradical polymerization initiator may also include the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass %. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, their total amount is preferably within the above range.

[Photoacid generator] In addition, in the composition of the present invention, it is also preferred to include a photoacid generator as a photosensitive agent. In addition, it is also possible to set the composition as follows: by containing a photoacid generator and a crosslinking agent other than the free radical crosslinking agent described later, for example, by using the acid generated in the exposed part to promote the crosslinking reaction of the crosslinking agent, the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinone diazonium compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimide sulfonates, oxime sulfonates, diazo disulfonates, disulfonates, and o-nitrobenzyl sulfonates.

Examples of the quinone diazide compound include a quinone diazide sulfonic acid bonded to a polyhydroxy compound via an ester bond, a quinone diazide sulfonic acid bonded to a polyamine compound via a sulfonamide bond, a quinone diazide sulfonic acid bonded to a polyhydroxy polyamine compound via an ester bond and a sulfonamide bond, etc. In the present invention, for example, preferably, 50 mol% or more of the functional groups of the polyhydroxy compound or polyamine compound are substituted with quinone diazide groups.

In the present invention, the quinone diazide can preferably use either 5-naphthoquinone diazide sulfonyl or 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl compound extends to the g-ray region of a mercury lamp and is suitable for g-ray exposure. In the present invention, the 4-naphthoquinone diazide sulfonyl compound or the 5-naphthoquinone diazide sulfonyl compound is preferably selected according to the exposure wavelength. Furthermore, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or it may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using such naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of such compounds, etc. can be cited.

Examples of the onium salt compound or the sulfonate salt compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but an oxime sulfonate compound represented by the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104) or the formula (OS-105) is preferred.

[Chemical formula 36]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are multiple X ³ , they may be the same or different. The alkyl group and alkoxy group in the above X ³ may have a substituent. As the alkyl group in the above X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in the above X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above X ³ , a chlorine atom or a fluorine atom is preferred. In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the multiple X ³ may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In the formula (OS-1), the compound wherein m3 is 3, ^X3 is methyl, the substitution position of ^X3 is an ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorthomethyl or p-tolyl is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[Chemical formula 37]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, a plurality of R ^s2 may exist and each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, a plurality of R ^s6 may exist and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 may have a substituent T.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and a hydrogen atom or an alkyl group is more preferred. In a compound, when there are two or more R ^s2 , one or two of them are preferably an alkyl group, an aryl group or a halogen atom, one is more preferably an alkyl group, an aryl group or a halogen atom, and one is particularly preferably an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formula (OS-103) to formula (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1. When Xs is S, ns is preferably 2. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent. In formula (OS-103) to formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 38]

In formula (OS-106) to formula (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 represents a hydrogen atom or a methyl group. In formula (OS-106) to formula (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and a hydrogen atom is preferably used.

In formula (OS-106) to formula (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z) of the oxime may be any one of them or a mixture. As specific examples of the oxime sulfonate compounds represented by the above-mentioned formula (OS-103) to formula (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification.

As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

[Chemical formula 39]

In formula (OS-101) or (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a cyano group, an aryl group, or a heteroaryl group. It is more preferred that R ^u9 is a cyano group or an aryl group, and it is further preferred that R ^u9 is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H-, or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonyl group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with a benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferred, and at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, the embodiment in which all of R ^u1 to R ^u4 are hydrogen atoms is preferred. The above substituents may further have substituents.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In addition, in the above oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or a mixture. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

In addition, commercial products may be used as the photoacid generator. Examples of commercial products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

As a more preferred example, the compound represented by the following structural formula can also be cited. [Chemical Formula 40]

As photoacid generators, organic halogenated compounds can also be used. As organic halogenated compounds, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, can be cited as trihalomethyl-substituted oxadiazole compounds: S-triazole compounds. More preferably, s-triazole derivatives in which at least one mono-, di- or trihalomethyl-substituted methyl group is bonded to the s-triazole ring can be cited. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazole, 2,4,6-tris(dichloromethyl)-s-triazole, 2,4,6-tris(trichloromethyl)-s-triazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazole, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazole can be cited. tris-1-nitropropene, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(4-naphthyl)-4,6-bis(trichloromethyl)-s-trisinyl, s-triazine, 2-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc.

As the photoacid generator, an organic borate compound can also be used. As the organic borate compound, specific examples thereof include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., the organic borate salts described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, the organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 The organic boron phosphonium complexes described in Japanese Patent Application Publication No. 9-188710, the organic boron transition metal coordination complexes described in Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, Japanese Patent Application Publication No. 7-292014, etc.

As the photoacid generator, a disulfide compound can also be used. Examples of the disulfide compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfide compounds.

Examples of the onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. al, Polymer, 21,423 (1980), the diazonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., the phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, the specifications of European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, the iodine salts described in Japanese Patent Laid-Open No. 2-150848 and Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390, 214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10 (6), 1307 (1977), selenium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), arsenic salts, pyridinium salts and other onium salts described in C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), etc.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 41] In the formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z11- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In terms of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar21 and Ar22 each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z21- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfuric acid ion. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, or carboxylic acid ions are preferred. In formula (RI-III), R31, R32, and R33 each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms and which may have 1 to 6 substituents. Preferably, an aryl group is preferred in terms of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z31- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In terms of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, or a carboxylic acid ion is preferred.

As a specific example, the following can be cited. [Chemical formula 42] [Chemical formula 43] [Chemical formula 44] [Chemical formula 45]

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

[Photobase generator] The photosensitive resin composition of the present invention may contain a photobase generator as a photosensitizer. By containing a photobase generator and a crosslinking agent described below in the photosensitive resin composition, it is possible to set the following state, for example, by promoting the cyclization of a specific resin and the crosslinking reaction of the crosslinking agent by the base generated in the exposed part, so that the exposed part is less likely to be removed by the developer than the non-exposed part. According to this state, a negative pattern can be obtained.

The photoalkali generator is not particularly limited as long as it generates alkali by exposure, and any known one can be used. For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S.Yoshitaka, J.Photopolym.Sci.Technol., 9, 13 (1996); K.Suyama, H.Araki, M.Shirai, J.Photopolym.Sci.Technol., 19, 81 (2006) state that transition metal compound complexes, substances having structures such as ammonium salts, substances whose amidine moieties are potentially oxidized by forming salts with carboxylic acids, ionic compounds whose base components are neutralized by forming salts, and non-ionic compounds whose base components are potentially oxidized by carbamate bonds or oxime bonds, such as carbamate derivatives, oxime ester derivatives, and acyl compounds. In the present invention, more preferred examples of the photoalkali generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, and the like.

The alkaline substance generated from the photoalkali generator is not particularly limited, and compounds having an amino group, especially polyamines such as monoamines and diamines, and amidines can be cited. From the perspective of the imidization rate, the alkaline substance preferably has a larger pKa in DMSO (dimethyl sulfoxide) of the conjugated acid. The pKa is preferably 1 or more, and 3 or more is more preferred. There is no particular upper limit for the pKa, and 20 or less is preferred. Here, the pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and can be found in Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; editor: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using ACD/pKa (manufactured by ACD/Labs) software were used as pKa.

From the perspective of storage stability of the photosensitive resin composition, it is preferable that the photoalkali generator does not contain salt in its structure, and it is preferable that the nitrogen atom of the alkali portion generated in the photoalkali generator has no charge. It is preferable that the generated alkali is potentially converted by covalent bonds, and it is preferable that the alkali generation mechanism is a mechanism in which the covalent bonds between the nitrogen atom of the generated alkali portion and the adjacent atom are cut to generate the alkali. If the photoalkali generator does not contain salt in its structure, the photoalkali generator can be made neutral, so that the solvent solubility is better and the shelf life is extended. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine. In addition, from the perspective of the chemical resistance of the pattern, a photobase generator containing a salt in its structure is preferred.

Furthermore, considering the above reasons, as a photoalkali generator, as mentioned above, the generated base is preferably potentially transformed using a covalent bond, and the generated base is preferably potentially transformed using an amide bond, a carbamate bond, or an oxime bond. As the photobase generator of the present invention, for example, a photobase generator having a cinnamylamide structure as disclosed in Japanese Patent Application Publication No. 2009-080452 and International Publication No. 2009/123122, a photobase generator having a carbamate structure as disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747, a photobase generator having an oxime structure or an aminoformyl oxime structure as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581, etc. can be cited, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, there can be cited compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of Japanese Patent Application Publication No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese Patent Application Publication No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Publication No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631.

In addition, commercial products can be used as photoalkali generators. Examples of commercial products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), and A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photobase generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The photobase generator may contain only one kind or two or more kinds. When two or more kinds of photobase generators are contained, the total amount thereof is preferably within the above range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the crosslinking agent also proceeds in the heating process described later, thereby further improving the solvent resistance.

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

When a thermal polymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass %. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, their total amount is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: by generating an acid by heating, the cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound is promoted.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a thermal acid generator is selected that does not generate acid during drying (pre-baking: about 70 to 140°C) after the composition is applied to the substrate, but generates acid during the final heating (hardening: about 100 to 400°C) after patterning in the subsequent exposure and development, it is preferred because the sensitivity drop during development can be suppressed. The thermal decomposition start temperature is obtained as the peak temperature of the lowest temperature heat peak when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 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 produce alkylsulfonic acids having 1 to 4 carbon atoms or halogenated alkylsulfonic acids having 1 to 4 carbon atoms are more preferred, such as (4-hydroxyphenyl)dimethylcoppersulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcoppersulfonate, benzyl(4-hydroxyphenyl)methylcoppersulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coppersulfonate, (4-hydroxyphenyl)dimethylcoppersulfonate, Preferred as the thermal acid generator are (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferred as a thermal acid generator.

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

<Onium salt> The photosensitive resin composition of the present invention may further contain an onium salt. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type of onium salt is not particularly specified, and ammonium salt, ammonium salt, stibnium salt, iodine salt or phosphonium salt can be preferably cited. Among them, ammonium salts or ammonium salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cationic part and an anionic part in the same molecular structure, or an intermolecular salt formed by ionic bonding of cationic molecules and anionic molecules of different molecules, but an intermolecular salt is preferred. Furthermore, in the photosensitive resin composition of the present invention, the cationic part or cationic molecule and the anionic part or anionic molecule may be bonded by ionic bonding or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a coronium cation, an iodine cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

The onium salt used in the present invention may be a thermal alkali generator described below. The thermal alkali generator refers to a compound that generates a base by heating, and examples thereof include compounds that generate a base when heated to 40°C or higher. As the onium salt, for example, onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262 may be cited. In addition, onium salts used in the field of polyimide precursors may be used without particular limitation.

When the photosensitive resin composition of the present invention contains an onium salt, the content of the onium salt is limited to the total solid content of the photosensitive resin composition of the present invention, preferably 0.1 to 50 mass %. The lower limit is 0.5 mass % or more, more preferably 0.85 mass % or more, and more preferably 1 mass %. The upper limit is 30 mass % or less, more preferably 20 mass % or less, and more preferably 10 mass % or less, and can also be 5 mass % or less, and can also be 4 mass % or less. The onium salt can be used in one or more than two kinds. When two or more kinds are used, the total amount is preferably within the above range.

<Thermal alkali generator> The photosensitive resin composition of the present invention may further contain a thermal alkali generator. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferred to contain a thermal alkali generator. Other thermal alkali generators may be compounds corresponding to the above-mentioned onium salts, or may be thermal alkali generators other than the above-mentioned onium salts. As thermal alkali generators other than the above-mentioned onium salts, non-ionic thermal alkali generators may be mentioned. As non-ionic thermal alkali generators, compounds represented by formula (B1) or formula (B2) may be mentioned. [Chemical formula 46]

In formula (B1) and formula (B2), ^Rb1 , ^Rb2 and ^Rb3 are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 will not be hydrogen atoms at the same time. Moreover, ^Rb1 , ^Rb2 and ^Rb3 will not all have carboxyl groups. In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when it forms an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and (B2), at least one of ^Rb1 , ^Rb2 and ^Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or arylalkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the scope of exerting the effects of the present invention. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. As the formed ring, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. ^Rb1 and ^Rb2 are particularly preferably linear, branched or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), arylalkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Arylalkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or arylalkoxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl, and arylalkoxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 47]

In the formula, ^Rb11 and ^Rb12 as well as ^Rb31 and ^Rb32 are the same as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within a range in which the effects of the present invention are exerted. Among them, ^Rb13 is preferably an arylalkyl group.

^Rb33 and ^Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

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

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 48]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

As specific examples of the compound serving as a thermal alkali generator among the above-mentioned onium salts or specific examples of the thermal alkali generator other than the above-mentioned onium salts, the following compounds can be cited.

[Chemical formula 49]

[Chemical formula 50]

[Chemical formula 51]

The content of other alkali generators is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is preferably 0.5% by mass or more, and 1% by mass or more is further preferred. The upper limit is preferably 30% by mass or less, and 20% by mass or less is further preferred. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent> The photosensitive resin composition of the present invention preferably contains a crosslinking agent. As the crosslinking agent, free radical crosslinking agents or other crosslinking agents can be cited.

<Free radical crosslinking agent> The photosensitive resin composition of the present invention preferably further contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the above-mentioned group containing an ethylenic unsaturated bond, there can be cited groups having an ethylenic unsaturated bond such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. Among them, as the above-mentioned group containing an ethylenic unsaturated bond, a (meth)acryloyl group is preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The free radical crosslinking agent can be any compound having one or more ethylenic unsaturated bonds, and compounds having two or more are more preferred. The compound having two ethylenic unsaturated bonds is preferably a compound having two of the above-mentioned groups containing ethylenic unsaturated bonds. In addition, from the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains three or more compounds having ethylenic unsaturated bonds as free radical crosslinking agents. As the above-mentioned compound having three or more ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is more preferred, a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenic unsaturated bonds is further preferred. Furthermore, the compound having more than 3 ethylenic unsaturated bonds is preferably a compound having more than 3 groups containing ethylenic unsaturated bonds, a compound having 3 to 15 groups is more preferably, a compound having 3 to 10 groups is further preferably, and a compound having 3 to 6 groups is particularly preferably. Furthermore, from the perspective of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains a compound having 2 ethylenic unsaturated bonds and a compound having 3 or more ethylenic unsaturated bonds.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, sulfhydryl groups, etc., and monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electron-withdrawing substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogeno groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Moreover, as another example, a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can also be used instead of the above unsaturated carboxylic acid. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated into this specification.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trihydroxymethylethane 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, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, and then (meth)acrylating the resulting mixture. Esterified compounds, such as urethane (meth) acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, there can be mentioned polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid.

Furthermore, as a preferred radical crosslinking agent other than the above, a compound having a fluorene ring and having two or more groups containing ethylenic unsaturated bonds, or a cardo resin described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, etc. can also be used.

As other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Association of Adhesion, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

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

In addition, compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof, in which ethylene oxide or propylene oxide is added to a polyfunctional alcohol and then (meth)acrylic acid is esterified, can also be used as a radical crosslinking agent.

In addition, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as a radical crosslinking agent, and these contents are incorporated into this specification.

As the free radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. The oligomer type of the same can also be used.

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four ethoxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentyloxy chains, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As free radical crosslinking agents, urethane acrylates 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, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent may also be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferably. It is particularly preferred that, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. include M-510 and M-520.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the free radical crosslinking agent is within the above range, the operability in production is excellent, and further, the developing property is excellent. In addition, the polymerizability is good. On the other hand, from the viewpoint of the developing speed during alkaline development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, the photosensitive resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hex ... Dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and bifunctional acrylate with carbamate bond, bifunctional methacrylate with carbamate bond. Two or more of these can be used in combination as needed. Furthermore, from the viewpoint of suppressing warping accompanying the control of the elastic modulus of the pattern, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

When a free radical crosslinking agent is contained, its content is preferably more than 0 mass % and less than 60 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

The free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used in combination, it is preferred that the total amount thereof be within the above range.

<Other crosslinking agents> The photosensitive resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. It is preferred that the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photosensitive agent, and it is preferred that the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of acids or bases. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator as a photosensitive agent in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group including hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which formaldehyde or formaldehyde and alcohol react with compounds containing amino groups such as melamine, acetylene urea, urea, alkyl urea, benzoguanamine, etc. to replace the hydrogen atom of the above amino group with hydroxymethyl or alkoxymethyl can be cited. The method for preparing these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds prepared by the above method. In addition, they can also be oligomers formed by self-condensation of hydroxymethyl groups of these compounds. A crosslinking agent using melamine as the above-mentioned amino group-containing compound is called a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group including urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group including acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylene urea, dihydroxymethylated acetylene urea, trihydroxymethylated acetylene urea, tetrahydroxymethylated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monoethoxymethylated acetylene urea, diethoxymethylated acetylene urea, triethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea, Acetylene urea-based crosslinking agents such as acetylene urea, monopropoxymethylated acetylene urea, dipropoxymethylated acetylene urea, tripropoxymethylated acetylene urea, tetrapropoxymethylated acetylene urea, monobutoxymethylated acetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea or tetrabutoxymethylated acetylene urea; Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea; Monohydroxymethyl ethylurea crosslinking agents such as methylated ethylurea or dihydroxymethylated ethylurea, monomethoxymethylated ethylurea, dimethoxymethylated ethylurea, monoethoxymethylated ethylurea, diethoxymethylated ethylurea, monopropoxymethylated ethylurea, dipropoxymethylated ethylurea, monobutoxymethylated ethylurea or dibutoxymethylated ethylurea; monohydroxymethylated propylurea, dihydroxymethylated propylurea, monomethoxymethylated propylurea , dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea and other propylene urea-based crosslinking agents; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) benzophenone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercial products may be used. Preferred commercial products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, hereinafter the same) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

In addition, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds and benzophenone compounds as other crosslinking agents.

[Epoxy compounds (compounds having epoxy groups)] As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C and do not produce dehydration reaction derived from crosslinking, so film shrinkage is not likely to occur. Therefore, containing epoxy compounds is effective for inhibiting low-temperature curing and warping of photosensitive resin compositions.

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite 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, EPICL ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds having an oxycyclobutyl group)] Examples of the oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[Benzotriazole compounds (compounds having a benzoxazolyl group)] Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, and further reduce thermal shrinkage to suppress the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (these are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), benzophenone adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

The content of other crosslinking agents relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %. Other crosslinking agents may be contained in one type or in two or more types. When two or more other crosslinking agents are contained, it is preferred that the total amount thereof is within the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure> From the viewpoint of improving the adhesion to the substrate of the obtained pattern, it is preferred that the photosensitive resin composition of the present invention further comprises at least one compound selected from the group consisting of compounds with sulfonamide structure and compounds with thiourea structure.

[Compounds having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical Formula 52] In formula (S-1), R represents a hydrogen atom or an organic group, and R may form a ring structure by bonding with other structures, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as ^R2 in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having one or more sulfonamide structures is preferred.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 53] In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. It is preferred that R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring.

Among these, the compounds wherein R ¹ is an aryl group and R ² and R ³ are independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 54] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may bond to form a ring, ^R4 may bond to other structures bonded by * to form a ring structure, ^R5 may bond to other structures bonded by * to form a ring structure, and * each independently represents a bonding site to other structures.

^R4 and ^R5 are preferably independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, and aryl groups having 6 to 12 carbon atoms are more preferred. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 55] In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 are synonymous with ^R4 and ^R5 in formula (T-1), and preferred embodiments are the same. In formula (T-2), ^R6 and ^R7 are preferably independently monovalent organic groups. In formula (T-2), preferred embodiments of monovalent organic groups in ^R6 and ^R7 are the same as preferred embodiments of monovalent organic groups in ^R4 and ^R5 in formula (T-1).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the photosensitive resin composition of the present invention is preferably 0.05-10 mass %, more preferably 0.1-5 mass %, and further preferably 0.2-3 mass %. The photosensitive resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is preferably within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

<Migration inhibitor> The photosensitive resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, it is possible to effectively inhibit metal ions originating from the metal layer (metal wiring) from migrating into the photosensitive film.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, trioxadiazole ring), thioureas, compounds having a thiohydrin group, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions may be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compound described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

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

The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferred that the total amount thereof is within the above range.

<Polymerization Inhibitor> The photosensitive resin composition of the present invention may also contain a polymerization inhibitor other than the above-mentioned hindered phenol compound.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, pyrogallol, 1,4-benzoquinone, diphenyl-p-benzoquinone, N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine, First tantalum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinium 1-oxyl free radical, phenanthridine, 1,1-diphenyl-2-picrylhydrazine, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, 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.

Furthermore, the following compounds can be used.

[Chemical formula 56]

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the photosensitive resin composition of the present invention can be 0.01 to 20.0 mass %, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass %.

The polymerization inhibitor may be one or more than one. When there are two or more polymerization inhibitors, the total amount thereof is preferably within the above range.

<Metal adhesion improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 57] As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-butylenepropyl methyldimethoxysilane, 3-butylenepropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding aid] As aluminum-based bonding aids, for example, tris(ethyl acetylacetate)aluminum, tris(acetylacetone)aluminum, ethyl acetylacetate aluminum diisopropylate, etc. can be cited.

As the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 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, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When using two or more kinds, it is better that the total is within the above range.

<Metallic Adhesion Improver> The photosensitive resin composition of the present invention preferably contains a metallic adhesion improver for improving adhesion to metal materials used in electrodes or wiring. As the metallic adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 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, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor containing the heterocyclic ring. By setting it above the above lower limit, the adhesion between the pattern and the metal layer after the heating process becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the hardened material after the heating process become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is better that the total is within the above range.

<Other additives> The photosensitive resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as sensitizers, alkaline compounds, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, etc. When such additives are formulated, the total amount thereof is preferably set to be less than 3% by weight of the solid content of the photosensitive resin composition.

[Sensitizer] The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a specific organic metal complex, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the specific organic metal complex, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids or bases. Examples of the sensitizer include michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-Dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl 3-Methoxycarbonyl-7-dimethylaminocoumarin, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin, N-Phenyl-N'-ethylethanolamine, N-Phenyldiethanolamine, N-p-Tolyldiethanolamine, N-Phenylethanolamine, 4-Phenylbenzophenone, Isoamyl dimethylaminobenzoate, Diethylaminobenzyl isopentyl ester, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As the sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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

[Alkaline compound] The photosensitive resin composition of the present invention may also contain an alkaline compound. The alkaline compound may also be a compound corresponding to the above-mentioned sensitizer, thermal acid generator, photoacid generator, or migration inhibitor. In the present invention, the alkaline compound is not particularly limited as long as it is alkaline in the curable resin composition, and the pKa in the conjugated acid DMSO is preferably 1.0 to 7.0, more preferably 1.5 to 7.0, and even more preferably 2.0 to 7.0. The alkaline compound is not particularly limited, and is preferably an amine compound, and a diamine compound or a tertiary amine compound is more preferably. Furthermore, the alkaline compound preferably contains at least one structure selected from the group including an aromatic amine structure and an alcoholic hydroxyl group, and the compound containing an aromatic amine structure and an alcoholic hydroxyl group is more preferred. In this specification, the aromatic amine structure refers to a structure in which an amine group or a substituted amine group is directly bonded to an aromatic ring, a structure in which a substituted amine group is bonded to an aromatic ring is preferred, and a structure in which a disubstituted amine group is bonded to an aromatic ring is more preferred. The substituent in the above-mentioned substituted amine group or disubstituted amine group is not particularly limited, but a alkyl group that can have a substituent is preferred, and a alkyl group that has at least an alcoholic hydroxyl group as a substituent is preferred. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is further preferred. The substituents in the disubstituted amino group may be the same or different. Specific examples of alkaline compounds include diethanolamine, N-phenyl-N'-ethylethanolamine, N-p-tolyldiethanolamine, or N-phenylethanolamine, but are not limited thereto.

When the photosensitive resin composition of the present invention contains an alkaline compound, the content of the alkaline compound is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.1 to 3 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The alkaline compound may be used alone or in combination of two or more.

[Chain transfer agent] The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Polymer Society, 2005), pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule can be used. These can generate free radicals by supplying hydrogen to low-activity free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be only one or more than two. When there are more than two chain transfer agents, it is preferred that the total amount thereof is within the above range.

[Surfactant] From the viewpoint of further improving coating properties, a surfactant can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content of each repeating unit (molar %), and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 58] In addition, the surfactant may also use compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219. As for fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups in the side chains may also be used as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation, may be cited.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. From the perspective of uniformity of the coating thickness or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon-based surfactants include PIONIN A-76, New Kalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the photosensitive resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, it is preferred that the total amount of the surfactant is within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, the photosensitive resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid or behenic acid amide so that it is unevenly distributed on the surface of the photosensitive resin composition during the drying process after coating.

Furthermore, the higher fatty acid derivatives may also include the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 10 mass %. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferred that the total amount is within the above range.

[Thermal polymerization initiator] The resin composition of the present invention may also contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be carried out, thereby further improving the solvent resistance.

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

When a thermal polymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 15 mass %. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, their total amount is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. If the average particle size of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may deteriorate. If the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of tris-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-1,2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and other mono(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)triol compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triol, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triol; 2,4-bis(2-hydroxy-4- tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota).

In the present invention, the aforementioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may contain or not contain an ultraviolet absorber, but when containing an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less relative to the total solid content of the composition of the present invention.

[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when hardening at a low temperature.

As the organic titanium compounds that can be used, there can be cited those in which an organic group is bonded to the titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: Among them, from the perspective of good storage stability of the negative photosensitive resin composition and the ability to obtain a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-pentanedioate) di(n-butoxy), titanium diisopropoxybis(2,4-pentanedioate), titanium diisopropoxybis(tetramethylpimelate), titanium diisopropoxybis(ethyl acetate), etc. II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyltitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc. III) Titanium cyclopentadienyl trimethoxide, for example, titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxy compounds: for example, titanium tris(dioctyl phosphate) isopropoxy, titanium tris(dodecylbenzene sulfonate) isopropoxy, etc. V) Titanium oxide compounds: for example, titanium bis(glutarate) oxide, titanium bis(tetramethylpimelate) oxide, titanium phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group including I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, bis(ethylacetyl acetate)diisopropoxytitanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the ductility of the film after curing or the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to a phenolic hydroxyl group (adjacent position) are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite. As commercially available antioxidants, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, ADKSTAB AO-330 (all manufactured by ADEKA CORPORATION) etc. can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, there can be cited compounds whose sites acting as antioxidants are protected by protective groups, and whose protective groups are released by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst, thereby acting as antioxidants. As potential antioxidants, there can be cited compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219. As commercially available products of potential antioxidants, there can be cited ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. Preferred examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

[Chemical formula 59]

In the general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, ^R6 represents an alkylene group having 2 or more carbon atoms, ^R7 represents an alkylene group having 2 or more carbon atoms, or a monovalent to tetravalent organic group containing at least one of an O atom and a N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group or the phenolic hydroxyl group of the resin. In addition, it can inhibit the oxidation of the metal by its rust-proofing effect on the metal material.

Since it can act on the resin and the metal material simultaneously, k is preferably an integer of 2 to 4. R ⁷ includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination thereof, and the like, and may further have a substituent. Among them, from the viewpoint of solubility in a developer or metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion by metal complex formation, -NH- is more preferred.

Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structure.

[Chemical formula 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

The amount of antioxidant added is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, relative to the resin. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the ductility characteristics after the reliability test or the adhesion to the metal material. When it is more than 10 parts by weight, it is possible to reduce the sensitivity of the resin composition due to the interaction with the photosensitive agent. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the photosensitive resin composition of the present invention is preferably less than 5 mass %, more preferably less than 1 mass %, and even more preferably less than 0.6 mass %. Methods for maintaining the water content include adjusting the humidity under storage conditions, reducing the porosity of the storage container, etc.

From the perspective of insulation, the metal content of the photosensitive resin 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. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When multiple metals are included, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities unintentionally contained in the photosensitive resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention; filtering the raw material constituting the photosensitive resin composition of the present invention with a filter; lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible.

In the photosensitive resin composition of the present invention, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, less than 300 mass ppm is more preferably, and less than 200 mass ppm is further preferably. Among them, the content of halogen ions is preferably less than 5 mass ppm, less than 1 mass ppm is more preferably, and less than 0.5 mass ppm is further preferably. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a container for storing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the photosensitive composition, it is also preferable to use a multi-layer bottle having an inner wall composed of six types of six layers of resin or a bottle having a seven-layer structure made of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Application of photosensitive resin composition> The photosensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer. In addition, it can also be used for forming an insulating film of a semiconductor device or forming a stress buffer film.

<Preparation of photosensitive resin composition> The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as dust or particles in the photosensitive resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. On the other hand, from the perspective of productivity, 5 μm or less is preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be pre-cleaned with an organic solvent. In the filter filtering process, multiple filters may be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. Also, filtering can be performed by pressurization. When filtering is performed by pressurization, the pressurization pressure is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is preferred, 0.03MPa or more and 0.9MPa or less is more preferred, and 0.05MPa or more and 0.7MPa or less is further preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

(Curing film, laminate, semiconductor device, and method for manufacturing the same) Next, the curing film, laminate, semiconductor device, and method for manufacturing the same are explained.

The cured film of the present invention is a cured film formed by curing the photosensitive resin composition of the present invention. The cured film is preferably a patterned cured film. The film thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more, or 1 μm or more. In addition, as an upper limit, it can be set to 100 μm or less, or 30 μm or less.

The cured film of the present invention can be laminated in two or more layers, and further laminated in 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes two or more layers of cured film and a metal layer between any of the above-mentioned cured films. For example, as a preferred embodiment, a laminate having a layered structure including at least three layers of a first cured film, a metal layer, and a second cured film laminated in sequence can be cited. The above-mentioned first cured film and the above-mentioned second cured film are both the cured films of the present invention. As a preferred embodiment, for example, the above-mentioned first cured film and the above-mentioned second cured film are both films formed by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention used for forming the first cured film and the photosensitive resin composition of the present invention used for forming the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a redistribution layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include patterning of sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for packaging purposes as described above by etching. For the use of these, for example, you can refer to Science and Technology Co., Ltd., "Advanced Functionality and Application Technology of Polyimide", April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, "Basics and Development of Polyimide Materials", November 2011, and Japan Polyimide and Aromatic Polymer Research Association, "Latest Polyimide Fundamentals and Applications", NTS Inc., August 2010, etc.

Furthermore, the cured film of the present invention can also be used in the production of printing plates such as offset printing plates and screen printing plates, in the etching of molded components, in the production of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film forming process of applying the photosensitive resin composition of the present invention to a substrate to form a film (resin film). The method for producing a cured film of the present invention preferably includes the above-mentioned film forming process, an exposure process of exposing the above-mentioned film, and a development process of developing the above-mentioned film. By the above-mentioned exposure process and development process, a pattern of the cured film can be obtained. Furthermore, the method for producing a cured film of the present invention preferably includes the above-mentioned film forming process and the above-mentioned development process as needed, and includes a heating process of heating the above-mentioned film at 50 to 450°C. Specifically, it is also preferred to include the following processes (a) to (d). (a) A film forming process of applying a photosensitive resin composition to a substrate to form a film (resin composition layer) (b) An exposure process of exposing the film after the film forming process (c) A developing process of developing the exposed film (d) A heating process of heating the developed film at 50 to 450°C By heating in the heating process, the resin layer hardened by exposure can be further hardened. In the heating process, for example, the hot alkali generator decomposes to obtain sufficient hardening properties.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. After forming a cured film according to the above-mentioned method for manufacturing a laminated body of the present embodiment, the process (a) or the processes (a) to (c) or the processes (a) to (d) are further performed again. In particular, it is preferred to perform the above-mentioned processes in sequence a plurality of times, for example 2 to 5 times (that is, a total of 3 to 6 times). By laminating the cured film in this way, a laminated body can be manufactured. In the present invention, it is particularly preferred to provide a metal layer on a portion provided with a cured film or between cured films, or on a portion provided with a cured film and between cured films. In addition, when manufacturing a laminate, it is not necessary to repeat all the processes (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film-forming process (layer-forming process)> The manufacturing method of the preferred embodiment of the present invention includes a film-forming process (layer-forming process) of applying a photosensitive resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately specified according to the purpose, and can be semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, evaporated film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc., without special restrictions. In addition, these substrates can be provided with a close contact layer or an oxide layer on the surface. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates and molded substrates are more preferred. In addition, the substrate may have a bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like on the surface. In addition, as the substrate, for example, a plate-shaped substrate (substrate) may be used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred. As for the size of the substrate, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

As a method of applying the photosensitive resin composition to the substrate, coating is preferred.

Specifically, as the applicable method, there can be exemplified dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By appropriately adjusting the solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, according to the viscosity of the photosensitive resin composition or the film thickness to be set, it is also preferred to apply at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In addition, in order to obtain uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method of transferring a coating film previously applied by the above-mentioned applying method and formed on a temporary support to a substrate can also be applied. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used in the present invention. Furthermore, a process of removing excess film can be performed at the end of the substrate. Examples of such processes include edge bead residue rinsing (EBR), air knife, back rinse, etc. Furthermore, the following pre-wetting process may be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process> The manufacturing method of the present invention may include a drying process for removing the solvent after the film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. The drying time may be 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

<Exposure process> The manufacturing method of the present invention may include an exposure process for exposing the above-mentioned film (resin composition layer). The exposure amount is not particularly specified as long as it can cure the photosensitive resin composition. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , in terms of exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, preferably 240 to 550 nm. In addition, the exposure light preferably includes light with a wavelength of 365 nm or a wavelength of 405 nm, and more preferably includes light with a wavelength of 405 nm.

Regarding the exposure wavelength, the following can be cited to explain the relationship between the wavelength and the light source: (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broadband (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), _F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser's second harmonic wave of 532nm and third harmonic wave of 355nm, etc. For the photosensitive resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. This can provide particularly high exposure sensitivity. In terms of operation and productivity, a wide (three wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred.

In addition, there is no particular limitation on the exposure method, as long as at least a portion of the film (photosensitive film) composed of a photosensitive resin composition is exposed, exposure using a mask, exposure based on a laser direct imaging method, etc. can be cited. In the present invention, the exposure in the exposure process is based on a laser direct imaging method, which is also one of the preferred aspects.

<Developing process> The manufacturing method of the present invention may include a developing process for developing (developing) the exposed film (resin composition layer). The unexposed portion (non-exposed portion) is removed by developing. The developing method is not particularly limited as long as the desired pattern can be formed. For example, it can be cited that the developer is sprayed from a nozzle, sprayed with a mist, and the substrate is immersed in the developer. Spraying from a nozzle can be preferably used. In the developing process, a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially stationary state, a process of vibrating the developer with ultrasound, etc., and a process of combining these can be adopted.

Development is performed using a developer. The developer can be used without particular restrictions as long as it can remove the unexposed portion (non-exposed portion). As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting a structural formula into ChemBioDraw as a calculated value.

When the developer contains an organic solvent, the organic solvent may be preferably 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, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate), , ethyl ethoxylate, etc.)), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl ester)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, 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, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably exemplified, and, as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably exemplified, as sulfoxides, for example, dimethyl sulfoxide is preferably exemplified, and, further, a mixture of these organic solvents is also preferably exemplified.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are preferred, and cyclopentanone is more preferred. In addition, when the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more.

When the developer contains an organic solvent, preferably 50% by mass or more of the developer is the organic solvent, more preferably 70% by mass or more of the developer is the organic solvent, and even more preferably 90% by mass or more of the developer is the organic solvent. In addition, the developer may contain 100% by mass of the organic solvent.

The developer may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be cited.

When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc. TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass % in the total mass of the developer.

[Developer supply method] The developer supply method is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate by immersion development, or continuously supplying the developer. The type of nozzle is not particularly limited, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, the method of supplying the developer with a vertical nozzle or the method of continuously supplying with a spray nozzle is preferred. From the perspective of developer permeability to the image area, the method of supplying with a spray nozzle is more preferred. In addition, a process can be adopted in which the developer is continuously supplied with a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a vertical nozzle again, and the substrate is rotated to remove the developer from the substrate, and this process can be repeated multiple times. In addition, as a method for supplying the developer in the developing process, a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially stationary state, a process of vibrating the developer on the substrate using ultrasound or the like, and a process combining these processes can be adopted.

The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing process is not particularly specified, but can generally be carried out at 10 to 45°C, preferably 20 to 40°C.

After the processing using the developer, rinsing can be further performed. Alternatively, a method such as supplying a rinsing solution while the developer in contact with the pattern is not completely dried can be adopted. It is preferred that the rinsing be performed in a solvent different from the developer. For example, a solvent contained in a photosensitive resin composition can be used for rinsing. When the developer is a developer containing an organic solvent, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), etc. can be cited as the rinsing solution, and PGMEA is preferred. Furthermore, as a rinsing solution for development based on a developer containing an alkaline aqueous solution, water is preferred. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly specified, but it is preferably 10 to 45°C, and more preferably 18 to 30°C.

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably 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, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example: 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2- The ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. Esters, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and, as sulfoxides, for example, dimethyl sulfoxide, and, as alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinse liquid contains an organic solvent, preferably 50 mass % or more of the rinse liquid is the organic solvent, more preferably 70 mass % or more of the rinse liquid is the organic solvent, and even more preferably 90 mass % or more of the rinse liquid is the organic solvent. In addition, the rinse liquid may contain 100 mass % of the organic solvent.

The rinse solution may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be cited.

[Method for supplying the rinse liquid] The method for supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, forming a liquid film of the rinse liquid on the substrate, supplying the rinse liquid to the substrate using a sprayer, and continuously supplying the rinse liquid to the substrate using a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing process is preferably a process in which a rinsing liquid is supplied or continuously supplied to the film after exposure using a vertical nozzle, and a process in which a rinsing liquid is supplied using a spray nozzle is more preferably a process. In addition, as a method for supplying the developer in the rinsing process, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept substantially stationary on the substrate, a process in which the rinsing liquid is vibrated on the substrate using ultrasound or the like, and a process in which these are combined can be adopted.

<Heating process> The manufacturing method of the present invention preferably includes a process (heating process) of heating the developed film at 50 to 450°C. It is preferred to include a heating process after the film formation process (layer formation process), drying process and development process. In the heating process, for example, a cyclization reaction as a specific resin precursor is carried out by decomposing the above-mentioned hot alkali generator to generate an alkali. In addition, the photosensitive resin composition of the present invention may also contain a free radical polymerizable compound other than the specific resin precursor, and the curing of the free radical polymerizable compound other than the unreacted specific resin precursor can also be carried out in the process. The heating temperature (maximum heating temperature) of the layer in the heating process is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, further preferably 160°C or higher, and further preferably 170°C or higher. As the upper limit, 500°C or lower is preferably, 450°C or lower is more preferably, 350°C or lower is further preferably, 250°C or lower is further preferably, and 220°C or lower is further preferably.

The heating is preferably performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured while preventing excessive volatility of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, the heating rate is preferably performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

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

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

In particular, when a multi-layer laminate is formed, from the viewpoint of the adhesion between the layers of the cured film, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. Although the reason is not clear, it is believed that the acetylene groups of the specific resin between the layers undergo cross-linking reactions at this temperature.

Heating can be performed in stages. For example, the following pretreatment process can be performed: heating from 25°C to 180°C at 3°C/min, maintaining at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, and maintaining at 200°C for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pretreatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. This pretreatment process can improve the properties of the membrane. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can also be set as a step of more than two stages, for example, pretreatment process 1 can be performed in the range of 100 to 150°C, and then pretreatment process 2 can be performed in the range of 150 to 200°C.

The heating and cooling can be further performed, and the cooling speed at this time is preferably 1 to 5°C/minute.

From the perspective of preventing the decomposition of a specific resin, it is better to perform the heating process in an atmosphere with a low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon. The oxygen concentration is preferably 50ppm (volume ratio) or less, and more preferably 20ppm (volume ratio) or less. The heating mechanism is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, and the like.

<Metal layer forming process> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the film (resin composition layer) after development.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be applied. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest wall portion.

<Layering process> The manufacturing method of the present invention preferably further includes a layering process.

The lamination process refers to a series of processes including (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process, which are performed again in order on the surface of the hardened film (resin layer) or metal layer. However, it is also possible to perform only the film formation process (a) repeatedly. In addition, it is also possible to perform the heating process (d) at the end or in the middle of the lamination. That is, it is possible to perform the processes (a) to (c) repeatedly for a specified number of times, and then perform heating (d), thereby curing the deposited resin composition layer in a lump. Furthermore, after the (c) developing process, the (e) metal layer forming process may be included. At this time, the heating in (d) may be performed each time, or the heating in (d) may be performed all at once after the layering is performed a specified number of times. Of course, the layering process may further appropriately include the above-mentioned drying process or heating process.

When a further layering process is performed after the layering process, a surface activation treatment process may be further performed after the heating process, after the exposure process, or after the metal layer forming process. As the surface activation treatment, plasma treatment may be exemplified.

The above-mentioned lamination process is preferably performed 2 to 20 times, 2 to 5 times, and 3 to 5 times. In addition, each layer in the lamination process can be the same layer in composition, shape, film thickness, etc., or different layers.

For example, a structure of two or more resin layers and twenty or less resin layers such as resin layer/metal layer/resin layer/resin layer/metal layer is preferred, a structure of three or more layers and seven or less resin layers is more preferred, and a structure of three or more layers and five or less resin layers is further preferred.

In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the photosensitive resin composition so as to cover the metal layer. Specifically, it is possible to cite an embodiment in which (a) film forming process, (b) exposure process, (c) development process, (e) metal layer forming process, and (d) heating process are repeated in this order, or (a) film forming process, (b) exposure process, (c) development process, and (e) metal layer forming process are repeated in this order and (d) heating process is provided at the end or in the middle. By alternately performing a lamination process of a resin composition layer (resin layer) and a metal layer forming process, it is possible to alternately laminarize a resin composition layer (resin layer) and a metal layer.

(Surface activation treatment process) The method for manufacturing a laminate of the present invention may include a surface activation treatment process for performing surface activation treatment on at least a portion of the above-mentioned metal layer and the photosensitive resin composition layer. The surface activation treatment process is usually performed after the metal layer forming process, but the metal layer forming process may also be performed after the above-mentioned exposure and development process and after the photosensitive resin composition layer is subjected to the surface activation treatment process. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed photosensitive resin composition layer, or may be performed on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or resin layer disposed on the surface subjected to surface activation treatment can be improved. Specifically, the surface activation treatment includes plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide film by immersion in hydrochloric acid aqueous solution and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, which are incorporated into this specification. [Example]

The present invention is further specifically described below with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

<Synthesis Example 1: Synthesis of polymer A-1> 46.96 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a separation flask, and 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and stirred at room temperature. While stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the heat due to the reaction was terminated, the mixture was naturally cooled to room temperature and left at room temperature for 16 hours. Next, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice cooling, and then a solution of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 30 minutes, 7.17 g of ethanol was added, and stirring was continued for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 716.21 g of ethanol to generate a precipitate consisting of a crude polymer. The resulting crude polymer was filtered out and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. The precipitate was filtered out and then vacuum dried to obtain a powdered polymer (polyimide precursor) P-1. The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polymer P-1 was measured by ¹ H-NMR (Nuclear Magnetic Resonance) method, and the result was 0.086 mmol/g.

<Synthesis Example 2: Synthesis of polymer P-2> A polymer (polyimide precursor) P-2 was synthesized in the same manner as in Synthesis Example 1, except that 46.91 g of ODPA was replaced with an equal molar amount of 4,4'-diphthalic dianhydride (BPDA). The total molar amount of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polymer P-2 was measured by ¹ H-NMR method and found to be 0.080 mmol/g.

<Synthesis Example 3: Synthesis of polymer P'-1> In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint equipped with an internal thermometer, 20.2 g (65.0 mmol) of 4,4'-oxydiphthalic dianhydride was suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were added, and stirred at 60°C for 18 hours. Then, after the mixture was cooled 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. Then, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, to the obtained transparent solution, a solution prepared by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour. 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. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C under reduced pressure for 3 days to obtain polymer P'-1. The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of polymer P'-1 was measured by ¹ H-NMR method and was 0.001 mmol/g.

<Synthesis Example 4: Synthesis of polymer P'-2> A polymer (polyimide precursor) P'-2 was synthesized in the same manner as in Synthesis Example 3, except that 20.2 g (65.0 mmol) of 4,4'-oxydiphthalic dianhydride was replaced with an equal molar amount of 4,4'-diphthalic dianhydride (BPDA). The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polymer P'-2 was measured by ¹ H-NMR method and found to be 0.001 mmol/g.

<Synthesis Example 5: Synthesis of polymer P-3> In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 65.56 g (179 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.48 g (10 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 300 g of N-methylpyrrolidone (NMP) while removing water. Then, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at 30°C for 2 hours. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 30°C for 2 hours. After stirring, the temperature was raised to 190°C while nitrogen was flowing at a flow rate of 200 ml/min, and the mixture was stirred for 6 hours. After the reaction solution was cooled to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise to the solution, and the mixture was stirred at 25°C for 2 hours, and then stirred at 60°C for 3 hours. The mixture was cooled to 25°C, 10 g of acetic acid was added, and the mixture was stirred at 25°C for 1 hour. After stirring, the mixture was precipitated in 2 liters of water/methanol = 75/25 (volume ratio), and stirred at 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain polyimide. The obtained polyimide was dried at 40°C under reduced pressure for 1 day to obtain P-3.

<Synthesis Example 6: Synthesis of polymer P-4> 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved by stirring in 400 g of N-methylpyrrolidone. Then, 12.1 g (153 mmol) of pyridine was added, and a solution prepared by dissolving 20.7 g (70.1 mmol) of 4,4'-oxydiphenylformyl chloride in 100 g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered and stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor was dried at 45°C for 3 days under reduced pressure to obtain polymer P-4.

<Synthesis Example 7: Synthesis of Polymer P-5> The above-mentioned polymer P-4 was dissolved in 300 g of N-methylpyrrolidone (NMP), and the temperature was raised to 190°C while nitrogen was flowing at a flow rate of 200 ml/min, and stirred for 6 hours. After stirring, it was precipitated in 2 liters of water/methanol = 75/25 (volume ratio) and stirred at 2,000 rpm for 30 minutes. The precipitated polybenzoxazole was filtered and obtained, and after washing with 1.5 liters of water, the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes and filtered again to obtain polybenzoxazole. The obtained polybenzoxazole was dried at 40°C under reduced pressure for 1 day to obtain polymer P-5.

<Synthesis Example 8: Synthesis of Polymer P-6> In Synthesis Example 1, except that 39.69 g of 2-hydroxyethyl methacrylate (HEMA) was replaced with 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 18.32 g of diethylene glycol monomethyl ether, the same method as Synthesis Example 1 was used to synthesize polymer P-6.

<Examples and Comparative Examples> In each example, the components listed in the following table were mixed to obtain each photosensitive resin composition. In each comparative example, the components listed in the following table were mixed to obtain each comparative composition. Specifically, the content of each component other than the solvent listed in the table is set to the amount (mass part) listed in each column in the table. The content of the solvent is set so that the solid concentration of each composition becomes "solid concentration (%)". The obtained photosensitive resin composition and comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[Table 1] Kind Embodiment 1 2 3 4 5 6 7 8 9 Resin P-1 41.5 - - - - 40.0 40.3 41.5 41.4 P-2 41.5 - - - - 40.0 40.3 41.5 41.4 P'-1 - - - - 41.0 - - - - P'-2 - - - - 41.0 - - - - P-3 - 80.7 - - - - - - - P-4 - - 74.8 - - - - - - P-5 - - - 73.1 - - - - - P-6 - - - - - - - - - Polymerization inhibitor A-1 - - - - - - - 0.1 - A-2 - - - - - - - - 0.1 A-3 - - - - - - - - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Migration inhibitors B-1 0.1 - - - - - - 0.1 - B-2 - - 0.1 - - - - - - Silane coupling agent C-1 - - - - - - - 0.5 - C-2 1.5 1.5 1.5 1.5 1.5 1.2 1.2 1 1.5 C-3 - - - - - 0.3 - - - C-4 - - - - - - 0.3 - - C-5 - - - - - - - - - Polymerization initiator D-1 - - - - - 0.5 - - - D-2 1 1.3 1.1 0.9 2.5 1 1.4 0.8 1.2 D-3 - - - - - 0.5 - - - D-4 - - - - - - 2 - - D-5 - - - - - - - - - Crosslinking agent E-1 8 8 16 16 8 8 8 7 8 E-2 - - - - - - - 1 - Thermoalkali generator F-1 - - 3 - - - - - - F-2 - 2 - - - - - - - F-3 - - - 2 - - - - - F-4 - - - - - 2 - - - Alkaline compounds G-1 6 6 3 6 6 6 6 6 5 G-2 - - - - - - - - 1 Other organometallic compounds H-1 - - - - - - - - - H-2 - - - - - - - - - H-3 - - - - - - - - - H-4 - - - - - - - - - H-5 - - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 15 15 15 15 15 15 15 Absorbance of membrane 0.312 0.335 0.301 0.277 0.223 0.304 0.345 0.292 0.331 Exposure conditions M M M M M M M M M Development conditions A B A B A A A A A Pattern shape A A A A A A A A A Resolution A B B B A A A A A Tightness A B B B B A A A A Mechanical properties A A A A A A A A A Drug resistance A A A A A A A A A

[Table 2] Kind Embodiment 10 11 12 13 14 15 16 17 18 Resin P-1 41.3 44.4 41.5 - 41.5 41.5 41.5 41.5 41.5 P-2 41.3 44.4 41.5 - 41.5 41.5 41.5 41.5 41.5 P'-1 - - - - - - - - - P'-2 - - - - - - - - - P-3 - - - - - - - - - P-4 - - - - - - - - - P-5 - - - - - - - - - P-6 - - - 82.9 - - - - - Polymerization inhibitor A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 0.1 - - - - - - - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Migration inhibitors B-1 - - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 B-2 - - - - - - - - - Silane coupling agent C-1 - - - - - - - - - C-2 1.5 1.5 1.5 1.5 - 1.5 1.5 1.5 1.5 C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 - - - - 1.5 - - - - Polymerization initiator D-1 - - - - - - - - - D-2 1.3 1.2 1 1 1 0.000 1 1 1 D-3 - - - - - - - - - D-4 - - - - - - - - - D-5 - - - - - 1 - - - Crosslinking agent E-1 8 8 8 8 8 8 8 8 8 E-2 - - - - - - - - - Thermoalkali generator F-1 - - - - - - - - - F-2 - - - - - - - - - F-3 - - - - - - - - - F-4 - - - - - - - - - Alkaline compounds G-1 5 - 6 6 6 6 6 6 6 G-2 1 - - - - - - - - Other organometallic compounds H-1 - - - - - - 1 - - H-2 - - - - - - - 1 - H-3 - - - - - - - - 1 H-4 - - - - - - - - - H-5 - - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 15 15 15 15 15 15 15 Absorbance of membrane 0.325 0.309 0.278 0.290 0.302 0.240 0.314 0.290 0.302 Exposure conditions M M D M M M M M M Development conditions A A A A A A A A A Pattern shape A A A A A A A A A Resolution A A A A A A A A A Tightness A A A A A A A A A Mechanical properties A A A A A A A A A Drug resistance A A A A A A A A A

[Table 3] Kind Embodiment Comparative example 19 20 twenty one twenty two twenty three 1 2 3 4 5 Resin P-1 41.5 41.5 41.5 41.5 41.4 39.8 - - 40.6 41.4 P-2 41.5 41.5 41.5 41.5 41.4 39.8 - - 40.6 41.4 P'-1 - - - - - - 39.8 40.1 - - P'-2 - - - - - - 39.8 40.1 - - P-3 - - - - - - - - - - P-4 - - - - - - - - - - P-5 - - - - - - - - - - P-6 - - - - - - - - - - Polymerization inhibitor A-1 - - - - - - - - - - A-2 - - - - 0.1 - - - - 0.1 A-3 - - - - - - - 0.1 - - A-4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - - 0.5 Migration inhibitors B-1 0.1 0.1 0.1 0.1 - 0.1 0.1 - 0.1 - B-2 - - - - - - - - - - Silane coupling agent C-1 - - - - - - - - - - C-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 C-3 - - - - - - - - - - C-4 - - - - - - - - - - C-5 - - - - - - - - - - Polymerization initiator D-1 - - - - - - - - - - D-2 1 1 1 1 8.0 0 1 0 0 10.0 D-3 - - - - - 1 1 1 1 - D-4 - - - - - 3.3 3.3 3.3 3.3 - D-5 - - - - - - - - - - Crosslinking agent E-1 8 8 8 8 8 8 8 8 8 8 E-2 - - - - - - - - - - Thermoalkali generator F-1 - - - - - - - - - - F-2 - - - - - - - - - - F-3 - - - - - - - - - - F-4 - - - - - - - - - - Alkaline compounds G-1 6 6 6 6 5 6 6 6 5 5 G-2 - - - - 1 - - - - 1 Other organometallic compounds H-1 - - - - - - - - - - H-2 - - - - - - - - - - H-3 - - - - - - - - - - H-4 1 - - - - - - - - - H-5 - 1 - - - - - - - - Solid content concentration (%) 44 44 44 44 44 44 44 44 44 44 Solvent S-1 80 80 80 80 80 80 80 80 80 80 S-2 20 20 20 20 20 20 20 20 20 20 Film thickness (μm) 15 15 20 30 15 15 15 15 15 15 Absorbance of membrane 0.290 0.314 0.278 0.278 0.586 0.276 0.170 0.120 0.276 0.663 Exposure conditions M M M M M M M M M M Development conditions A A A A A A A A A A Pattern shape A A A A A C B B C B Resolution A A A A A B D E B C Tightness A A A A A B C C B B Mechanical properties A A A A A C B B C C Drug resistance A A A A A C B B D C

The details of each ingredient listed in the table are as follows.

[Resin] ・P-1~P-6, P'-1~P'-2: polymers P-1~P-6, P'-1~P'-2 obtained from the above synthesis example

[Polymerization inhibitor] ・A-1 to A-4: Compounds having the following structures [Chemical formula 64]

<Migration inhibitor> ・B-1~B-2: Compounds with the following structures [Chemical formula 65]

[Silane coupling agent (metal adhesion enhancer)] ・C-1 to C-5: Compounds with the following structure [Chemical formula 66] In the above structure, Me represents a methyl group, and Et represents an ethyl group.

[Photoradical polymerization initiator] ・D-1 to D-4: Compounds with the following structures ・D-5: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium [chemical formula 67] D-2 and D-5 are compounds having photo-radical polymerization initiation capability.

(Crosslinking agent) ・E-1~E-2: Compounds with the following structures [Chemical formula 68]

[Thermoalkali generator] ・F-1 to F-4: Compounds with the following structure [Chemical formula 69]

[Alkaline compounds] ・G-1~G-2: Compounds with the following structure [Chemical formula 70]

[Other organic metal compounds] ・H-1: Titanium tetraisopropoxide (Matsumoto Fine Chemical Co. Ltd.) ・H-2: Titanium diisopropoxide (acetylacetonate) (Matsumoto Fine Chemical Co. Ltd.) ・H-3 to H-5: Compounds with the following structure [Chemical formula 71]

[Solvent] ・S-1: N-methyl-2-pyrrolidone ・S-2: Ethyl lactate

<Evaluation> [Measurement of absorbance] In each embodiment or comparative example, the prepared photosensitive resin composition or comparative composition was applied to a glass substrate by spin coating. The substrate was heated to 100°C at a heating rate of 10°C/min on a heating plate in the atmosphere, and then maintained at 100°C for 5 minutes to form a film with a thickness of 15 μm. The absorbance of the film at a wavelength of 405 nm was measured using an ultraviolet-visible spectrophotometer (UH-4150, manufactured by Hitachi High-Tech Science Corporation.) and recorded in the column "Absorbance of film" in the table.

[Evaluation of pattern shape] In each embodiment and comparative example, each photosensitive resin composition or comparative composition was applied (coated) in layers on a silicon wafer by spin coating to form a composition layer. In each embodiment and comparative example, the silicon wafer to which the obtained composition layer was applied was dried on a heating plate at 100°C for 5 minutes to form a resin layer having a thickness described in the column of "film thickness (μm)" in the table on the silicon wafer. In the example where "M" was described in the exposure condition, the resin layer on the silicon wafer was exposed using an h-ray stepper. Exposure was performed through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). The exposure amount was appropriately set to obtain a pattern of a resin layer with a line width of 10μm after the development described below. In the example where "D" is recorded in the exposure condition, exposure was performed using a direct exposure device (AdTech DE-6UH III). The exposure wavelength was set to 405nm. Laser direct imaging exposure was performed so that the exposed part became a line part in a 1:1 line and space pattern with a width of 10μm. The exposure amount was appropriately set to obtain a pattern of a resin layer with a line width of 10μm after the development described below. After the above exposure, in the example described as "A" in the column of "Developing Conditions", cyclopentanone was used for 60 seconds of development, and propylene glycol monomethyl ether acetate (PGMEA) was used for 20 seconds of rinsing, thereby obtaining the line and space pattern of the resin layer after exposure. In the example described as "B" in the column of "Developing Conditions", a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution was used as a developer for 5 minutes of development, and pure water was used for rinsing, thereby obtaining the line and space pattern of the resin layer after exposure. The above line and space pattern was heated at a heating rate of 10°C/min in a nitrogen environment, and heated at 230°C for 3 hours, thereby obtaining a cured film. The silicon wafer on which the obtained cured film was formed was cut perpendicularly to the line and space pattern of the cured film to expose the pattern cross section. The pattern cross section of the line and space pattern was observed at a magnification of 200 times using an optical microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, in each embodiment and comparative example, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Pattern Shape" column in the table. In this evaluation, it can be said that the taper angle does not exceed 90°, and the cross-sectional shape of the pattern is not a necked shape. The closer the taper angle is to 90°, the better the pattern shape is. -Evaluation criteria- A: The taper angle is 85° or more and 90° or less. B: The taper angle is 80° or more and less than 85°. C: The taper angle is less than 80°, or the cross-sectional shape of the pattern is an inverted cone with a taper angle exceeding 90°, or the cross-sectional shape of the pattern is a constricted neck shape.

[Evaluation of resolution] In each of the embodiments and comparative examples, each photosensitive resin composition or comparative composition was applied (coated) in layers on a silicon wafer by spin coating to form a composition layer. In each of the embodiments and comparative examples, the silicon wafer to which the obtained composition layer was applied was dried on a heating plate at 100°C for 5 minutes to form a resin layer having a thickness described in the column of "Film thickness (μm)" in the table on the silicon wafer. In the example where "M" was described in the exposure condition, the resin layer on the silicon wafer was exposed using an h-ray stepper. Exposure was performed through a mask of a fuse box with a width of 5μm to 25μm and a scale of 1μm. The exposure amount was set to the exposure amount that minimizes the minimum line width described below. In the example where "D" is recorded in the exposure condition, laser direct imaging exposure was performed using a direct exposure device (AdTech DE-6UH III) so that the exposure portion became a line portion in a 1:1 line and space pattern with a scale of 1μm and a width of 5μm to 25μm. The exposure wavelength was set to 405nm. The exposure amount was set to the exposure amount that minimizes the minimum line width described below. After the above exposure, in the example where "A" is recorded in the column of "Developing Conditions", cyclopentanone is used for 60 seconds of development, and propylene glycol monomethyl ether acetate (PGMEA) is used for 20 seconds of rinsing, thereby obtaining the line and space pattern of the resin layer after exposure. In the example where "B" is recorded in the column of "Developing Conditions", a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution is used as a developer for 5 minutes of development, and pure water is used for rinsing, thereby obtaining the line and space pattern of the resin layer after exposure. Among the above line and space patterns, the line width of the smallest line pattern in which the silicon wafer is exposed between the line patterns is regarded as the "minimum line width", and it is evaluated according to the following evaluation criteria. It can be said that the smaller the line width, the better the resolution. For example, it means that the width of the metal wiring formed in the subsequent plating process can be miniaturized, which is a better result. The measurement limit is 5μm. The evaluation results are recorded in the "Resolution" column in the table. -Evaluation criteria- A: The minimum line width is 5μm or more and less than 8μm. B: The minimum line width is 8μm or more and less than 10μm. C: The minimum line width is 10μm or more and less than 12μm. D: The minimum line width is 12μm or more and less than 15μm. E: The minimum line width is 15μm or more.

[Evaluation of Adhesion] In each of the embodiments and comparative examples, each photosensitive resin composition or each comparative composition was applied (coated) in layers on a copper substrate by spin coating to form a resin composition layer. In each of the embodiments and comparative examples, the copper substrate to which the obtained composition layer was applied was dried on a heating plate at 100°C for 5 minutes, thereby forming a resin layer having a thickness described in the column of "Film Thickness (μm)" in the table on the copper substrate. In the example where "M" was described in the exposure condition, the resin layer on the copper substrate was exposed using an h-ray stepper. Exposure was performed through a mask having a square non-masking portion of 100μm square. In order to obtain a 100μm square pattern of the resin layer after the development described below, the exposure amount was appropriately set. In the example where "D" is recorded in the exposure condition, exposure was performed using a direct exposure device (AdTech DE-6UH III). The exposure wavelength was set to 405nm. Laser direct imaging exposure was performed so that the exposure portion became a 100μm square square. In order to obtain a 100μm square pattern of the resin layer after the development described below, the exposure amount was appropriately set. After the above exposure, in the example where "A" is recorded in the column of "Developing Conditions", cyclopentanone is used for 60 seconds of development, and propylene glycol monomethyl ether acetate (PGMEA) is used for 20 seconds of rinsing to obtain a 100μm square square resin layer pattern. In the example where "B" is recorded in the column of "Developing Conditions", a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution is used as a developer for 5 minutes of development, and pure water is used for rinsing to obtain a 100μm square square resin layer pattern. The above pattern was heated at a heating rate of 10°C/min in a nitrogen environment, and heated at 230°C for 3 hours to obtain a cured film. The shear force of the cured film was measured using an adhesion tester (CondorSigma, manufactured by XYZTEC) at 25°C and 65% relative humidity (RH), and the evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion" column in the table. The greater the shear force, the better the adhesion (copper adhesion) of the cured film.

-Evaluation criteria- A: Shear force exceeds 40gf. B: Shear force exceeds 30gf and is less than 40gf. C: Shear force is less than 30gf. In addition, 1gf is 0.00980665N.

[Evaluation of Mechanical Properties] In each embodiment and comparative example, each photosensitive resin composition or comparative composition was applied (coated) in layers on a silicon wafer by spin coating to form a composition layer. The silicon wafer to which the obtained composition layer was applied was dried on a heating plate at 100°C for 5 minutes to form a photosensitive resin composition layer having a thickness described in the "Film Thickness (μm)" column in the table on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 400mJ/ ^cm2 using a wideband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01). Exposure was performed through a photomask, and the shape of the above-mentioned photomask was set to a shape that could obtain a pattern with a sample width of 2 mm and a sample length of 50 mm after development described below. After exposure, in the example where "A" was recorded in the column of "Development Conditions", cyclohexanone was used as a developer for 60 seconds, and PGMEA was used for rinsing. In the example where "B" was recorded in the column of "Development Conditions", a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution was used as a developer, and development was performed for 5 minutes, and pure water was used for rinsing. The developed photosensitive resin composition layer (resin layer) was heated at a rate of 5°C/min in a nitrogen environment, and after reaching 230°C, it was heated for 3 hours. The heated resin layer was immersed in a 3 mass% hydrofluoric acid solution, and the resin layer was peeled off from a silicon wafer to obtain a resin film. The resin film peeled off from the silicon wafer was subjected to a tensile strength test. The test used a tensile testing machine (Tensilon) with a crosshead speed of 300 mm/min, a sample width of 2 mm, and a sample length of 50 mm. The test was conducted in the longitudinal direction of the film at 25°C and 65% RH (relative humidity) in accordance with JIS-K6251 (Japanese Industrial Standards). The elongation of the sample when the sample broke during shearing (elongation at break) was measured 10 times each, and the arithmetic mean of the elongation at break obtained in the 10 measurements was calculated. The results were evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Mechanical Properties" column in the table. -Evaluation Criteria- A: The above arithmetic mean is 60% or more. B: The above arithmetic mean is 50% or more and less than 60%. C: The above arithmetic mean is less than 50%.

[Evaluation of chemical resistance] During exposure, the entire surface was exposed without using a mask, and development was omitted for the sake of simplicity. A hardened film was formed on the silicon wafer in the same manner as in the evaluation of mechanical properties. Without peeling the hardened film from the silicon wafer, the hardened film and the silicon wafer were immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: A mixture of 90:10 (mass ratio) of dimethyl sulfoxide (DMSO) and 25 mass % tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The resin layer was immersed in the chemical solution at 75°C for 15 minutes, and the film thickness before and after immersion was compared to calculate the dissolution rate (nm/minute). The evaluation is conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Drug Resistance" column in the table. The lower the dissolution rate, the better the drug resistance. -Evaluation Criteria- A: Dissolution rate is less than 200nm/min. B: Dissolution rate is 200nm/min or more and less than 300nm/min. C: Dissolution rate is 300nm/min or more and less than 400nm/min. D: Dissolution rate is 400nm/min or more.

According to the above results, it can be seen that the pattern obtained by the photosensitive resin composition of the present invention has excellent pattern shape.

<Example 101> The photosensitive resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 100°C for 5 minutes to form a photosensitive film with a film thickness of 20μm, and then exposed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, heating was performed at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds to obtain a layer pattern. Then, in a nitrogen atmosphere, the temperature was raised at a rate of 10°C/min to 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and the results confirmed that there were no problems with the operation.

without.

Claims (17)

A photosensitive resin composition comprises: a polyimide precursor; an organic metal complex having photopolymerization initiation ability; and a hindered phenol compound, wherein when a film having a thickness of 15 μm is formed by heating at 100° C. for 5 minutes, the absorbance of the film at a wavelength of 405 nm is 0.2 to 0.6, and the polyimide precursor comprises at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-6).

In formula (2-1) to formula (2-6), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. The photosensitive resin composition as described in claim 1, wherein the aforementioned organometallic complex has photo-radical polymerization initiation energy. A photosensitive resin composition comprises: a polyimide precursor; an organic metal complex having photo-radical polymerization initiation energy; and a hindered phenol compound, for forming a film composed of the photosensitive resin composition, wherein the film thickness of the film is greater than 15 μm, and the absorbance of the film at a wavelength of 405 nm is 0.2-0.6, wherein the polyimide precursor comprises at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-6),

In formula (2-1) to formula (2-6), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. A photosensitive resin composition as described in claim 1 or claim 3, wherein the metal in the aforementioned organometallic complex is titanium. The photosensitive resin composition as described in claim 1 or claim 3, wherein the aforementioned organometallic complex is a metallocene compound. The photosensitive resin composition as described in claim 1 or claim 3, wherein the content of the aforementioned organometallic complex is 0.5 mass % to 5.0 mass % relative to the total solid content of the photosensitive resin composition. The photosensitive resin composition as described in claim 1 or claim 3 further comprises a sensitizer. A photosensitive resin composition as described in claim 1 or claim 3, wherein the aforementioned polyimide precursor is a polyimide precursor comprising at least one of a cyclic imide structure and a cyclic isoimide structure, and the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1g of the polyimide precursor is 0.08mmol/g~1.68mmol/g. The photosensitive resin composition as described in claim 1 or claim 3 is used to form a photosensitive film for negative type development. The photosensitive resin composition as described in claim 1 or claim 3 is used to form an interlayer insulating film for a redistribution layer. A cured film, which is formed by curing the photosensitive resin composition as described in any one of claim 1 to claim 10. A laminate comprising two or more layers of the hardened films as described in claim 11, and a metal layer between any of the hardened films. A method for manufacturing a hardened film, comprising: a film forming process, wherein a photosensitive resin composition as described in any one of claim 1 to claim 10 is applied to a substrate to form a film. The method for manufacturing a hardened film as described in claim 13 includes: an exposure process for exposing the aforementioned film; and a development process for developing the aforementioned film. The method for manufacturing a hardened film as described in claim 13, wherein the aforementioned exposure is based on laser direct imaging. The method for manufacturing a hardened film as described in claim 13 includes: a heating process, which is to heat the aforementioned film at 50°C~450°C. A semiconductor device comprising the hardened film as described in claim 11.