TWI845667B - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate. The curable resin composition comprises at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and has two or more aromatic rings directly bonded to substituted vinyl groups in the molecule.

Description

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

The present invention relates to a curable resin composition, a cured film, a laminate, a method for manufacturing the cured film, and a semiconductor device.

The resin obtained by curing by cyclizing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as "hybrid ring-containing polymer precursor") has excellent heat resistance and insulation properties, and can be used for various purposes. The above-mentioned use is not particularly limited, but if the semiconductor device for actual mounting is taken as an example, the use as a material or protective film of an insulating film or a sealing material can be cited. In addition, it is also used as a base film or a cover film of a flexible substrate.

For example, in the above-mentioned application, the hybrid ring-containing polymer precursor is used in the form of a curable resin composition containing the hybrid ring-containing polymer precursor. The curable resin composition is applied to a substrate by coating, etc., and then the hybrid ring-containing polymer precursor is cyclized by heating, etc., so that a cured resin can be formed on the substrate. The curable resin composition can be applied by a known coating method, etc., so it can be said that the curable resin composition has excellent manufacturing adaptability, such as high degree of freedom in designing the shape, size, and application position of the curable resin composition to be applied. In addition to the high performance of polyimide resins, the industrial application of curable resin compositions containing heterocyclic polymer precursors is expected to expand from the perspective of excellent manufacturing adaptability.

For example, Patent Document 1 describes a method for manufacturing a partition wall including a specific process for dividing a storage space formed between a first electrode layer stack and a second electrode layer stack, wherein the storage space contains an immiscible polar liquid and a non-polar liquid. Patent Document 2 describes a photosensitive polymer composition comprising (a) a polyimide precursor and a polyimide, (b) a photopolymerization initiator, and (c) an aromatic diamine compound.

[Patent Document 1] Japanese Patent Publication No. 2017-015811 [Patent Document 2] Japanese Patent Publication No. 2006-201670

In the formation of a cured film formed by curing a curable resin composition containing a heterocyclic polymer precursor such as a polyimide precursor, for example, when a laminate is prepared by further applying and curing the curable resin composition on the cured film, there is a case where the first formed cured film contacts with a developer or other components. Therefore, in the curable resin composition, for example, from the viewpoint of resistance to a developer of the cured film or suppression of dissolution of the cured film due to contact with other components, it is desired to provide a curable resin composition in which the obtained cured film has excellent chemical resistance.

The object of the present invention is to provide a curable resin composition having a cured film having excellent chemical resistance, a cured film formed by curing the curable 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 curable resin composition comprising: at least one polymer precursor selected from the group consisting of polyimide precursors and benzoxazole precursors and a compound having two or more aromatic rings directly bonded to a vinyl group that may be substituted in the molecule. ＜2＞ The curable resin composition as described in ＜1＞, wherein the compound having two or more aromatic rings directly bonded to a vinyl group that may be substituted in the molecule is a compound represented by the following formula (1-1): [Chemical Formula 1] In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a heterocyclic group, and groups bonded to 2 or more of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom or a methyl group, and m represents an integer of 2 to 6. <3> The curable resin composition as described in <2>, wherein the above Z comprises a ring selected from the group consisting of a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an iso-oxazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, an indole ring, an indazole ring, a benzophenone ring, a As the heterocyclic ring in the heterocyclic group, at least one heterocyclic ring selected from the group consisting of an imidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, a benzoselenazole ring, a benzothiadiazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a triazole ring, a quinoline ring, a quinazoline ring, a furan ring, and a thiophene ring is used. <4> The curable resin composition according to <2> or <3>, wherein the ratio of the ^sp3 carbon to the number of all atoms except the hydrogen atom in Z in the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is 0.2 to 0.4. <5> The curable resin composition as described in any one of <1> to <4>, wherein the molecular weight of the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is 200 to 2,000. <6> The curable resin composition as described in any one of <1> to <5>, further comprising a photo-radical polymerization initiator. <7> The curable resin composition as described in any one of <1> to <6>, further comprising an onium salt. <8> The curable resin composition as described in any one of <1> to <7>, comprising a polyimide precursor as the polymer precursor. <9> The curable resin composition as described in <8>, wherein the polyimide precursor has a repeating unit represented by the following formula (1): [Chemical Formula 2] In formula (1), ^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. <10> The curable resin composition as described in <9>, wherein at least one of ^R113 and ^R114 in the above formula (1) contains a radical polymerizable group. <11> The curable resin composition as described in any one of <1> to <10>, which is used for forming an interlayer insulating film for a redistribution layer. <12> A cured film formed by curing the curable resin composition as described in any one of <1> to <11>. <13> A laminate comprising two or more layers of the cured film described in <12>, wherein a metal layer is included between any of the cured films. <14> A method for producing a cured film, comprising a film forming process of applying the curable resin composition described in any one of <1> to <11> to a substrate to form a film. <15> The method for producing a cured film as described in <14>, comprising an exposure process of exposing the film and a development process of developing the film. <16> The method for producing a cured film as described in <14> or <15>, comprising a heating process of heating the film at 50 to 450°C. <17> A semiconductor device comprising the cured film described in <12> or the laminated body described in <13>. [Effect of the Invention]

According to the present invention, there are provided a curable resin composition having a cured film having excellent chemical resistance, a cured film formed by curing the curable 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 embodiments indicated. In this specification, the numerical range indicated by the symbol "～" indicates a range including the numerical values recorded before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only indicates an independent process, but also includes processes that cannot be clearly distinguished from other processes as long as the desired effect of the process can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and 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, "exposure" includes exposure using particle beams such as electron beams and ion beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, there can be cited the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "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 means the total mass of the components excluding the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is 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 based on gel permeation chromatography (GPC measurement) and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting the laminate is recorded as "up" or "down", it is sufficient that other layers exist 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 a third element may be further sandwiched 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 "up", or when there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is called "up", and the opposite direction is called "down". In addition, the setting of these up and down directions is for the convenience of this specification. In actual forms, the "up" direction in this specification may also be different from the vertical up direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds that meet the requirements of the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds that meet the requirements of the component. In this specification, unless otherwise specified, the temperature is 23°C and the air pressure is 101,325Pa (1 atmosphere). In this specification, a combination of a preferred embodiment is a more preferred embodiment.

(Curing resin composition) The curable resin composition of the present invention comprises at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a compound having two or more aromatic rings directly bonded by substituted vinyl groups in the molecule. In addition, the curable resin composition of the present invention preferably further comprises a photo-radical polymerization initiator described below.

The cured film obtained by the curable resin composition of the present invention has excellent chemical resistance. The mechanism for achieving the above effect is not yet clear, but it can be inferred as follows.

Conventionally, a compound having a radical polymerizable group is used in a curable resin composition containing a heterocyclic polymer precursor, and the radical polymerizable group is radically polymerized by exposure, heating, etc. to obtain a cured film. Among them, the curable resin composition of the present invention contains a compound having two or more aromatic rings directly bonded to a vinyl group that may be substituted in the molecule. It is believed that when the curable resin composition is radically polymerized, the obtained cured film contains a structure of a vinyl polymerized group directly bonded to the aromatic ring and a polyimide ring structure. Since there is an interaction between the structure of the vinyl polymerization and the polyimide ring structure, it is believed that the cured film formed by the curable resin composition of the present invention has low permeability to organic solvents, low solubility in organic solvents, etc., and excellent chemical resistance. In addition, it is known that the above-mentioned free radical polymerization is inhibited in the presence of oxygen, and it is believed that when the above-mentioned exposure, heating, etc. are performed in the presence of oxygen, a compound having an unreacted free radical polymerizable group remains in the cured film. However, the curable resin composition of the present invention contains a compound having two or more aromatic rings directly bonded by a substituted vinyl group in the molecule. The substituted vinyl group directly bonded to the aromatic ring is not easily inhibited by polymerization in the presence of oxygen, so it is believed that even in the presence of oxygen, free radical polymerization during exposure, heating, etc. proceeds rapidly. As a result, the amount of unreacted free radical polymerizable groups in the cured film is reduced, so according to the curable resin composition of the present invention, it is believed that a cured film with low permeability and solubility in organic solvents can be obtained. In addition, as described above, the vinyl group directly bonded to the aromatic ring is not easily inhibited from polymerization in the presence of oxygen, so it is believed that the exposure sensitivity of the curable resin composition of the present invention is also excellent.

Among them, in Patent Documents 1 or 2, there is no description or suggestion of a curable resin composition containing a heterocyclic polymer precursor and a compound having two or more aromatic rings directly bonded by substituted vinyl groups in the molecule. The components contained in the curable resin composition of the present invention are described in detail below.

<Hybrid ring-containing polymer precursor> The curable resin composition of the present invention contains a heterocyclic polymer precursor. As the above-mentioned heterocyclic polymer precursor, the curable resin composition of the present invention contains at least one precursor selected from the group including polyimide precursors and polybenzoxazole precursors, and preferably contains a polyimide precursor.

[Polyimide Precursor] From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the following formula (1). [Chemical Formula 3]

In formula (1), ^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 the formula (1), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, and an oxygen atom is preferably an oxygen atom.

-R ¹¹¹ - R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group combining two or more of these groups. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups are preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred.

R ¹¹¹ in formula (1) 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. The diamine may be used alone or in combination of two or more.

Specifically, the diamine is preferably a diamine containing a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of two or more of these groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[Chemical formula 4]

In the formula, A is preferably a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHC(=O)-, or a combination of two or more of these groups. It is more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, _-O- , -C(=O)-, -S-, and S(=O) _2- . It is further preferably a divalent group selected from the group consisting of _-CH2- , -O-, -S-, -S(=O)2-, -C( _CF3 ) _2- , and -C( _CH3 ) _2- .

As the diamine, specifically, there can be mentioned 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexyl Methane or isophoronediamine; meta-phenylenediamine or para-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone or 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl Aminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 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)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminobiphenyl Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane Aminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoro Propane, 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- At least one of the following diamines: 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotoluidine and 4,4’-diaminoquaternaryl.

Furthermore, the diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical formula 5]

[Chemical formula 6]

As a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, or both, and more preferably, it is a diamine that does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) The present invention may include, but is not limited to, EDR-176, D-200, D-400, D-2000, D-4000 (the above trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc.

The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176 are shown below.

[Chemical formula 7]

In the above, x, y, and z are arithmetic means.

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ in formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. Ar ⁰ is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L ⁰ represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO-, or a group in which two or more of these groups are combined. The preferred range of L ⁰ has the same meaning as that of A above.

From the viewpoint of i-ray transmittance, R ¹¹¹ in formula (1) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[Chemical formula 8]

In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and * independently represents a bonding site with other structures.

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[Chemical formula 9]

In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound that gives the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 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.

-R ¹¹⁵ - R ¹¹⁵ in formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).

[Chemical formula 10]

R ¹¹² has the same meaning as A, and the preferred range is also the same. * Each independently represents a bonding site with other structures.

As the tetravalent organic group represented by R ¹¹⁵ in formula (1), specifically, there can be mentioned the tetracarboxylic acid residue remaining after removing the acid dianhydride group 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 a compound represented by the following formula (7).

[Chemical formula 11]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5 - at least one of 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 their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) are also mentioned as preferable examples.

[Chemical formula 12]

-R ¹¹³ and R ¹¹⁴ - R ¹¹³ and R ¹¹⁴ in formula (1) 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 free radical polymerizable group, and it is more preferred that both contain a free radical polymerizable group. The free radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a free radical, and a group having an ethylenic unsaturated bond can be cited as a preferred example.

Examples of the group having an ethylenic unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acryloyl group, and a group represented by the following formula (III).

[Chemical formula 13]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

In formula (III), ^R201 represents an alkylene group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly)oxyalkylene group represents an oxyalkylene group or a polyoxyalkylene group. Preferred examples of ^R201 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, and _-CH2CH (OH) _CH2- . More preferred examples are an ethylene group, a propylene group, a trimethylene group, and _-CH2CH (OH) _CH2- . It is particularly preferred that R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethyl group. In formula (III), * represents a bonding site with other structures. As a preferred embodiment of the polyimide precursor in the present invention, the monovalent organic group of R ¹¹³ or R ¹¹⁴ includes a group having 1, 2 or 3 acid groups, preferably an aliphatic group, an aromatic group and an aralkyl group having 1 acid group. Specifically, an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms can be cited. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be cited. It is preferred that the acid group is a hydroxy group. That is, it is preferred that R ¹¹³ or R ¹¹⁴ is a group having a hydroxy group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility in a developer solution can be preferably used.

From the viewpoint of solubility in aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a benzyl group, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, ^R113 or ^R114 is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferred, and an alkyl group substituted with an aromatic group is more preferred.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (or more than 3 when cyclic). The alkyl group may be any one of a straight chain, a branched chain, or a cyclic chain. Examples of the straight chain or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic alkyl group include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, borndiyl, bicyclohexyl and pinenyl. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group as described below is preferred.

The aromatic group may be specifically a substituted or unsubstituted aromatic alkyl group (as the ring structure constituting the group, there may be mentioned a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentylene ring, an indene ring, an azulene ring, a heptylene ring, an indenyl ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a chrysene ring, a tris-extended benzene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (as the ring structure constituting the group, there may be mentioned a fluorene ring, a pyrrole ring, etc. , furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyridine ring, pyrrolidine ring, pyrimidine ring, pyrimidine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolyl ring, quinoline ring, phthaloyl ring, naphthridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthracene ring, chromene ring, pyrrolidine ring, phenanthryl ring, phenanthryl ring or phenanthryl ring).

In addition, it is also preferred that the polyimide precursor has fluorine atoms in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is practically 50% by mass or less.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or formula (1-B).

[Chemical formula 14]

^A11 and ^A12 represent an oxygen atom or -NH-, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of ^R113 and ^R114 is preferably a group containing a free radical polymerizable group, and more preferably a free radical polymerizable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), wherein oxygen atom is more preferred.

The bonding position of the carbonyl group to the benzene ring is preferably 4, 5, 3', or 4' in formula (1-A). In formula (1-B), 1, 2, 4, or 5 is preferred.

In the polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. Furthermore, the repeating unit represented by formula (1) may contain structural isomers. Furthermore, in addition to the repeating unit of the above formula (1), the polyimide precursor may also contain other types of repeating units.

As an embodiment of the polyimide precursor of the present invention, 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total repeating units are repeating units represented by formula (1). The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, further preferably 4,000 to 25,000, and particularly preferably 4,000 to 24,000.

The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3. In this specification, the molecular weight dispersion is the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

The polyimide precursor can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, the polyimide precursor is obtained by halogenating the dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the diamine with the dicarboxylic acid.

In the method for producing a polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more.

The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone.

When manufacturing the polyimide precursor, a process including solid precipitation is preferred. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby enabling solid precipitation.

[Polybenzoxazole precursor] The polybenzoxazole precursor preferably comprises a repeating unit represented by the following formula (2). [Chemical Formula 15]

In formula (2), ^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.

-R ¹²¹ - In formula (2), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms) is preferred. As an aromatic group constituting R ¹²¹ , R ¹¹¹ of the above formula (1) can be cited as an example. As the above aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxydiphenylformyl chloride.

-R ¹²² - In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (1) above, and the preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

-R ¹²³ and R ¹²⁴ - R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meanings as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the repeating units of the above formula (2), the polybenzoxazole precursor may also contain other types of repeating units.

From the viewpoint of being able to suppress the warping of the cured film caused by ring closure, the polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[Chemical formula 16]

Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R ^2s is a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferred that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

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. The molecular weight can be determined by gel permeation chromatography, which is commonly used. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced, and the effect of suppressing warping and the effect of improving solubility can be achieved.

When the polybenzoxazole precursor contains a diamine residue represented by formula (SL) as another type of repeating unit, it is preferred to further contain a tetracarboxylic acid residue remaining after removing the dianhydride group from tetracarboxylic dianhydride as a repeating unit from the viewpoint of improving the alkali solubility of the curable resin composition. Examples of such a tetracarboxylic acid residue include R ¹¹⁵ in formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the heterocyclic polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and still further preferably 70% by mass or more, relative to the total solid content of the curable resin composition. In addition, the content of the heterocyclic polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, still further preferably 97% by mass or less, and still further preferably 95% by mass or less, relative to the total solid content of the curable resin composition.

The curable resin composition of the present invention may contain only one heterocyclic polymer precursor or two or more. When two or more heterocyclic polymer precursors are contained, the total amount is preferably within the above range.

<Compounds having two or more aromatic rings directly bonded to a vinyl group which may be substituted> The curable resin composition of the present invention contains a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted (hereinafter also referred to as a "specific polymerizable compound").

[Aromatic ring directly bonded to a vinyl group which may be substituted] In this specification, an aromatic ring directly bonded to a vinyl group which may be substituted means a structure in which one carbon atom in the double bond of the vinyl group which may be substituted is directly bonded to an aromatic ring structure. The aromatic ring may have a well-known substituent such as an alkyl group or a halogen group. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring, or an aromatic heterocyclic ring or an aliphatic heterocyclic ring may be condensed on the aromatic hydrocarbon ring or the aromatic heterocyclic ring. Furthermore, the aromatic hydrocarbon rings, aliphatic hydrocarbon rings, aromatic heterocyclic rings or aliphatic heterocyclic rings may have known substituents such as alkyl groups and halogen groups, respectively. The aromatic ring in the aromatic ring directly bonded to the vinyl group which may be substituted is preferably an aromatic hydrocarbon ring, and a benzene ring is more preferably. That is, the specific polymerizable compound preferably contains vinylphenyl as a group containing the above-mentioned aromatic ring directly bonded to the vinyl group. The number of aromatic rings directly bonded to the vinyl group in the specific polymerizable compound is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. Furthermore, the specific polymerizable compound may have an ethylenically unsaturated group other than the vinyl group in the aromatic ring to which the above-mentioned vinyl group is directly bonded, but as a preferred embodiment of the specific polymerizable compound, an embodiment having no ethylenically unsaturated group other than the above-mentioned vinyl group can be cited. Furthermore, it is preferred that the vinyl group in the aromatic ring to which the vinyl group in the specific polymerizable compound is directly bonded has free radical polymerizability. Furthermore, as a substituent in the vinyl group that may be substituted, an alkyl group can be cited, for example, an embodiment in which the α hydrogen in the vinyl group is substituted by a methyl group can be cited.

The amount (molar amount) of the vinyl group in 1 g of the specific polymerizable compound is preferably 2 to 8 mmol/g, more preferably 3 to 7 mmol/g.

[Compound represented by formula (1-1)] The specific polymerizable compound is preferably a compound represented by the following formula (1-1). [Chemical formula 17] In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a heterocyclic group, and these groups bonding to 2 or more groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When ^RA exists in plural numbers, the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom or a methyl group, and m represents an integer of 2 to 6. The hydrogen atom in the benzene ring in formula (1-1) may be substituted by a substituent. The substituent is not particularly limited as long as the object of the present invention can be achieved, and a known substituent can be used. In addition, an aspect without such a substituent is also a preferred aspect in the present invention.

-Z- As the divalent or higher aliphatic saturated alkyl group in Z, an aliphatic saturated alkyl group having 1 to 100 carbon atoms is preferred, and an aliphatic saturated alkyl group having 2 to 30 carbon atoms is more preferred. The above-mentioned divalent or higher aliphatic saturated alkyl group is preferably a 2-20-valent aliphatic saturated alkyl group, preferably a 2-10-valent aliphatic saturated alkyl group, and more preferably a 2-6-valent aliphatic saturated alkyl group. In addition, the above-mentioned divalent or higher aliphatic saturated alkyl group may have a known substituent as long as the effect of the present invention can be obtained. As the divalent or higher aliphatic unsaturated alkyl group in Z, an aliphatic unsaturated alkyl group having 2 to 100 carbon atoms is preferred, and an aliphatic unsaturated alkyl group having 2 to 30 carbon atoms is more preferred. The divalent or higher aliphatic unsaturated alkyl group is preferably a 2 to 20-valent aliphatic unsaturated alkyl group, preferably a 2 to 10-valent aliphatic unsaturated alkyl group, and more preferably a 2 to 6-valent aliphatic unsaturated alkyl group. In addition, the divalent or higher aliphatic unsaturated alkyl group may have a known substituent as long as the effect of the present invention can be obtained. In addition, in formula (1-1), Z is preferably a group containing at least one selected from the group including a cycloalkyl group and a heterocycloalkyl group.

As the alkyl group in Z, a 2- to 4-valent group obtained by removing 2- to 4 hydrogen atoms from the alkyl ring is preferred. As the number of ring members of the alkyl ring in the alkyl group in Z, 6 to 20 are preferred, 6 to 12 are more preferred, and 6 is further preferred. As the alkyl ring in the alkyl group in Z, an aromatic alkyl ring is preferred, and a benzene ring is more preferred.

As the heterocyclic group in Z, a 2-4 valent group obtained by removing 2-4 hydrogen atoms from the heterocyclic ring is preferred. As the heteroatom in the above heterocyclic ring, an oxygen atom, a nitrogen atom, a sulfur atom or a selenium atom is preferred. Moreover, the number of heteroatoms contained in the heterocyclic ring as a ring member is preferably 1-4. As the heterocyclic ring in the heterocyclic group in Z, an aromatic heterocyclic ring is preferred, an aromatic heterocyclic ring having 5-20 ring members is preferred, and an aromatic heterocyclic ring having 5-20 ring members is more preferred. The above-mentioned heterocyclic ring may be a condensed ring of multiple heterocyclic rings, or a condensed ring of a heterocyclic ring and an aromatic hydrocarbon ring. When the heterocyclic ring is a condensed ring, the number of ring members of the heterocyclic ring as a single ring contained in the condensed ring is preferably 5 to 6. As the divalent or higher saturated aliphatic hydrocarbon group in Z, a saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms is more preferred. As long as the effect of the present invention can be obtained, the above-mentioned saturated aliphatic hydrocarbon group may have a known substituent. As the unsaturated aliphatic hydrocarbon group having a valence of 2 or more in Z, an unsaturated aliphatic hydrocarbon group having 2 to 100 carbon atoms is preferred, and an unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms is more preferred. As long as the effect of the present invention can be obtained, the above-mentioned saturated aliphatic hydrocarbon group may have a known substituent.

From the perspective of intermolecular interaction, as a heterocyclic ring in the heterocyclic group, Z includes a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isothiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, an indole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzothiazole ring, a benzoselenazole ring, a benzothiadiazole ring, a pyridine ring, a pyrimidine ... Preferably, at least one heterocyclic ring is selected from the group consisting of a thiazolidine ring, a trithiazolidine ring, a quinoline ring, a quinoxaline ring, a furan ring and a thiophene ring. More preferably, at least one heterocyclic ring is selected from the group consisting of a pyrazole ring, an imidazole ring, a triazole ring, an isothiazolidine ring, an isothiazolidine ring, a thiazolidine ring, a thiatriazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a trithiazolidine ring, a quinoline ring, a quinoxaline ring, a furan ring and a thiophene ring.

Furthermore, Z is preferably a group represented by the following formula (Z-1) or formula (Z-2). [Chemical Formula 18] In formula (Z-1) or formula (Z-2), A1 and A2 each independently represent a alkyl group or a heterocyclic group, ^LZ1 to ^LZ5 each independently represent a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, a alkylene group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a heterocyclic group, and groups bonded to two or more of these groups, ^RA represents a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, and * each independently represents a bonding site to the benzene ring in formula (1-1).

＜＜A1 and A2＞＞ In formula (Z-1) or formula (Z-2), A1 and A2 are preferably independently an aromatic hydrocarbon ring group or an aromatic heterocyclic group. As the aromatic hydrocarbon ring in the above aromatic hydrocarbon ring group, a benzene ring is preferred. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isothiazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, an indole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, a benzoselenazole ring, a benzothiadiazole ring, a pyridine ring, A tantalum ring, a pyrimidine ring, a pyridine ring, a triazole ring, a quinoline ring, a quinoxaline ring, a furan ring or a thiophene ring is preferred, and a pyrazole ring, an imidazole ring, a triazole ring, an isoxazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, a pyridine ring, a tantalum ring, a pyrimidine ring, a pyridine ring, a triazole ring, a quinoline ring, a quinoxaline ring, a furan ring or a thiophene ring is more preferred.

In formula (Z-1) or (Z-2), ^LZ1 to ^LZ5 independently represent a divalent linking group selected from the group consisting of an alkylene group, a divalent aromatic cyclic group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a divalent aromatic heterocyclic group, and a group in which two or more of these groups are bonded. A divalent linking group in which two or more alkylene groups, divalent aromatic cyclic groups, -O-, -S-, and -N( ^RA )- are bonded is more preferred. ^RA in formula (Z-1) or (Z-2) has the same meaning as ^RA in formula (1-1), and the preferred embodiment is also the same. The divalent aromatic alkyl ring is preferably a phenyl ring. The divalent aromatic heterocyclic group is preferably a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isothiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, an indole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzothiazole ring, a benzoselenazole ring, a benzothiadiazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a trithiazole ring, a quinoline ring, or a pyrimidine ring. The present invention is preferably a divalent aromatic heterocyclic group obtained by removing two hydrogen atoms from a pyrazole ring, an imidazole ring, a triazole ring, an isoazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, a thiatriazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a triazole ring, a quinoline ring, a quinoline ring, a furan ring or a thiophene ring.

^-RA- In formula (1-1), ^RA represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a hydrogen atom.

-R ¹ - In formula (1-1), R ¹ represents a hydrogen atom or a methyl group, and a hydrogen atom is more preferred.

-m- In formula (1-1), m represents an integer from 2 to 6, preferably an integer from 2 to 4, and more preferably 2 or 3.

In the specific polymerizable compound, the ratio of ^sp3 carbon to the number of all atoms excluding hydrogen atoms in Z is preferably 0.2 to 0.4. The ratio of ^sp3 carbon to the number of all atoms excluding hydrogen atoms in Z is a value calculated by "the number of ^sp3 carbons included in Z/the number of all atoms excluding hydrogen atoms in Z".

[Molecular weight] The molecular weight of the compound represented by formula (1-1) can be determined by considering the cyclization temperature, volatility, etc., preferably 200 or more, more preferably 250 or more, more preferably 300 or more, and even more preferably 400 or more. There is no particular upper limit, but 2,000 or less is preferred.

[Specific Examples] The following compounds can be cited as specific polymerizable compounds, but are not limited thereto. [Chemical Formula 19] [Chemical formula 20] [Chemical formula 21]

[Synthesis method] For example, the specific polymerizable compound can be synthesized by the following method. For example, compounds such as (B-1) to (B-5), (B-8) or (B-12) can be obtained by a known thioetherification reaction such as a reaction between a polyvalent alkyl compound and halogenated methylstyrene. Compounds such as (B-6), (B-7), (B-9) or (B-11) can be obtained by a known etherification reaction such as a reaction between a polyol compound and halogenated methylstyrene or halogenated styrene. Compounds such as (B-10) can be obtained by a known esterification reaction such as a reaction between a polyol compound and a vinyl benzoic acid halide.

[Content] From the perspective of improving the storage stability of the curable composition and the elongation at break of the obtained cured film, the content of the specific polymerizable compound is preferably 0.005 to 50% by mass relative to the total solid content of the curable resin composition. The lower limit is more preferably 0.05% by mass, more preferably 0.5% by mass, and particularly preferably 1% by mass. From the perspective of the mechanical properties of the cured film, the upper limit of the above content is more preferably 40% by mass, more preferably 30% by mass, and particularly preferably 20% by mass. The curable resin composition of the present invention may contain only one specific polymerizable compound or two or more. When two or more are contained, it is preferred that the total amount be within the above range.

<Onium salt> The curable resin composition of the present invention preferably contains an onium salt. The type of onium salt is not particularly limited, and preferably includes ammonium salts, imide salts, cobalt salts, iodine salts, or phosphonium salts. Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodine salts, or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, the onium salt is a salt of a cation and 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 having ionic bonding between cationic molecules and anionic molecules of different molecules, and an intermolecular salt is preferred. Furthermore, in the curable 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 also be a thermal alkali generator described below. The thermal alkali generator refers to a compound that generates an alkali by heating, and for example, a compound that generates an alkali when heated to 40°C or higher can be cited.

[Ammonium salt] In the present invention, ammonium salt refers to a salt of ammonium cations and anions.

-Ammonium cation- As the ammonium cation, the fourth ammonium cation is preferred. Furthermore, as the ammonium cation, the cation represented by the following formula (101) is preferred. [Chemical formula 22] In formula (101), R ¹ to R ⁴ each independently represents a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to form a ring.

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

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2). [Chemical Formula 23]

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

-Anions- As the anion in the ammonium salt, one selected from the group consisting of carboxylate anions, phenol anions, phosphate anions, and sulfate anions is preferred, and carboxylate anions are more preferred from the perspective of both stability and thermal decomposition of the salt. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylate anions. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. According to this aspect, the stability, curability, and developability of the curable resin composition can be further improved. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developing properties of the curable resin composition can be further improved.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 24] In formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group refers to a group whose Hammett substituent constant σm represents a positive value. σm is described in detail in Yufu Mitsuno's General Commentary, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (σm=0.06), Ac group (σm=0.38), MeOC (=O) group (σm=0.37), MeC (=O) CH=CH group (σm=0.21), PhC (=O) group (σm=0.34), H ₂ NC (=O) CH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group. (The same shall apply hereinafter).

EWG is preferably a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 25] In formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical Formula 26] In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NR ^X -, and a combination thereof, and ^RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion and an oxalate anion.

From the viewpoint that the cyclization of the specific precursor is easy to proceed at low temperature and the storage stability of the curable resin composition is easy to improve, the onium salt in the present invention contains ammonium cations as cations and the onium salt contains anions with a pKa (pKaH) of 2.5 or less of the conjugated acid as anions. It is more preferable to contain anions with a pKa of 1.8 or less. The lower limit of the above pKa is not particularly limited. From the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor is improved, -3 or more is preferred, and -2 or more is more preferred. As the pKa, the values described 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) can be referred to. For compounds not described in these references, values calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software were used.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 27]

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

-Imine cation- As the imine cation, pyridinium cation is preferred. Also, as the imine cation, a cation represented by the following formula (102) is preferred. [Chemical Formula 28]

In formula (102), ^R5 and ^R6 each independently represent a hydrogen atom or a alkyl group, ^R7 represents a alkyl group, and at least two of ^R5 to ^R7 may be bonded to form a ring. In formula (102), the meanings of ^R5 and ^R6 are the same as those of ^R1 to ^R4 in formula (101), and preferred embodiments are also the same. In formula (102), it is preferred that ^R7 is bonded to at least one of ^R5 and ^R6 to form a ring. The ring may contain a heteroatom. As the heteroatom, a nitrogen atom may be cited. In addition, as the ring, a pyridine ring is preferred.

The imide cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical Formula 29] In formula (Y1-3) to (Y1-5), ^R101 represents an n-valent organic group, ^R5 has the same meaning as ^R5 in formula (102), ^R7 has the same meaning as ^R7 in formula (102), and n and m represent integers greater than 1. In formula (Y1-3), ^R101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which they are bonded, and more preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, or a group obtained by removing n hydrogen atoms from benzene or naphthalene. In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and more preferably 1. In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and more preferably 1.

As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 30]

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

- Copper cation - As the copper cation, a third copper cation is preferred, and a triaryl copper cation is more preferred. Furthermore, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical Formula 31]

In formula (103), R ⁸ to R ¹⁰ each independently represents a alkyl group. R ⁸ to R ¹⁰ each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups. From the viewpoint of synthetic suitability, it is preferred that they are the same group.

As specific examples of the cobalt salt, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 32]

[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiment is also the same.

-Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 33]

In formula (104), R ¹¹ and R ¹² each independently represent a alkyl group. R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹¹ and R ¹² may be the same group or different groups. From the perspective of synthetic suitability, it is preferred that they are the same group.

As specific examples of iodine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 34]

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

-Phosphonium cation- As the phosphonium cation, a tetraalkylphosphonium cation is preferred, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 35]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a alkyl group. R ¹³ to R ¹⁶ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups. From the viewpoint of synthetic suitability, it is preferred that they are the same group.

As specific examples of phosphonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 36]

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is preferably 0.5 mass % or more, 0.85 mass % or more is further preferred, and 1 mass % or more is further preferred. The upper limit is preferably 30 mass % or less, 20 mass % or less is further preferred, and 10 mass % or less is further preferred. It can be 5 mass % or less, and can also be 4 mass % or less. One or more onium salts can be used. When two or more are used, the total amount is preferably within the above range.

<Thermoalkali generator> The curable resin composition of the present invention may contain a thermoalkali generator. The thermoalkali generator may be a compound that meets the above-mentioned onium salt, or may be another thermoalkali generator other than the above-mentioned onium salt. As another thermoalkali generator, a non-ionic thermoalkali generator may be mentioned. As a non-ionic thermoalkali generator, a compound represented by formula (B1) or formula (B2) may be mentioned. [Chemical Formula 37]

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 do not have a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which the three bonds of the trivalent nitrogen atom are covalently bonded to the carbon atom of the hydrocarbon system. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when it forms an amide group together with the 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 either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring of 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 preferred. The monocyclic ring is preferably a cyclohexane ring and 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 aralkyl 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 range in which the effects of the present invention are exerted. ^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. In particular, ^Rb1 and ^Rb2 are 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.

As Rb ³ , there can be mentioned 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), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (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 aralkyloxy (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), aralkenyl, and aralkyloxy are preferred. ^Rb3 may further have a substituent within the range in which the effects of the present invention are 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 38]

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings 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 aralkyl 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 aralkyl 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 aralkyl 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 alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), alkenyl (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and aryl is preferred.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 39]

^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), aralkyl 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 alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), alkenyl (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein aryl 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 as a thermoalkali generator or other specific examples of a thermoalkali generator, the following compounds can be cited.

[Chemical formula 40]

[Chemical formula 41]

[Chemical formula 42]

The content of the alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. 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.

<Photopolymerization initiator> The curable resin composition of the present invention preferably contains a photopolymerization initiator. 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, an activator that reacts with a photoexcited sensitizer to generate active radicals can be used.

The photo-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 by a known method. For example, it is preferably measured by a UV-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, metallocene compounds, organic boron compounds, iron aromatic 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.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. 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 also 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, a compound described in Japanese Patent Application Laid-Open 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 Corporation) can also be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

As the photoradical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Among oxime compounds, the exposure tolerance (exposure margin) is wide and they also function as photohardening accelerators, so they are particularly preferred.

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: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the curable resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group represented by >C=N-O-C(=O)- in the molecule.

[Chemical formula 43]

Among the commercial 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 be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-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, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

More 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. It is further preferred to select at least one compound from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and oxime compounds are further preferred.

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

[Chemical formula 44]

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group substituted by at least one of an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, R ¹⁰¹ is a group represented by formula (II), or is the same group as R ¹⁰⁰ , and R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[Chemical formula 45]

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 include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content 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 % relative to the total solid content of the curable resin composition of the present invention. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount thereof is preferably within the above range.

<Thermal polymerization initiator> As a polymerization initiator, the curable resin composition of the present invention may include a thermal polymerization initiator, and in particular, may include a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the heterocyclic polymer precursor can be cyclized and the polymerization reaction of the heterocyclic polymer precursor can be carried out, thereby achieving a higher level of heat 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 free radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass %. The thermal free radical polymerization initiator may be contained in one type or in two or more types. When two or more thermal free radical polymerization initiators are contained, the total amount thereof is preferably within the above range.

<Polymerizable compound> [Free radical polymerizable compound] The curable resin composition of the present invention preferably further contains a polymerizable compound. The "polymerizable compound" in the present invention is defined as a polymerizable compound other than compounds that meet the above-mentioned specific polymerizable compound. As the polymerizable compound, a free radical polymerizable compound can be used. A free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. can be cited. The free radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferred.

The number of radical polymerizable groups possessed by the radical polymerizable compound may be 1 or 2 or more. The radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably has 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

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

From the viewpoint of developing properties, the curable resin composition of the present invention preferably contains at least one radically polymerizable compound having two or more radical polymerizable groups, and more preferably contains at least one radically polymerizable compound having three or more functional groups. In addition, it may be a mixture of a radically polymerizable compound having two or more functional groups and a radically polymerizable compound having three or more functional groups. For example, the number of functional groups of a polymerizable monomer having two or more functional groups means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of free radical polymerizable compounds 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 an affinity substituent such as a hydroxyl group, an amino group, or a thiohydride group with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Moreover, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and the substitution reaction products of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, instead of the above-mentioned unsaturated carboxylic acid, a compound group substituted by unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

In addition, as for the radical polymerizable compound, a compound having a boiling point of 100°C or higher under normal pressure is also preferred. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol hexa(meth)acrylate, hexanediol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylate. Compounds of the present invention, (meth)acrylic acid urethanes 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 resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

Furthermore, as a preferred radical polymerizable compound 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 be used.

Furthermore, 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, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" 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, the following compounds described as formula (1) and formula (2) together with their specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radical polymerizable compound, and these contents are incorporated into the present specification.

As the radical polymerizable compound, 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 above can also be used.

As commercially available products of the radical polymerizable compound, for example, SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy 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 (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION.), etc.

As free radical polymerizable compounds, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those 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. Furthermore, as the radical polymerizable compound, 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 polymerizable compound may be a free radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical polymerizable compounds having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Particularly preferred is a free radical polymerizable compound having an acid group by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, in which the aliphatic polyhydroxy compound is a compound of neopentyl triol or dipentyl triol. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited.

The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. As long as the acid value of the radical polymerizable compound is within the above range, the operability in production is excellent, and further the developing property is excellent. In addition, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of suppressing warping accompanying control of elastic modulus of the cured film, the curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional free radical polymerizable compound, (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-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

[Polymerizable compounds other than the above-mentioned free radical polymerizable compounds] The resin composition of the present invention may also contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; cyclohexane compounds; and benzophenone compounds.

-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group- As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

[Chemical formula 46] (In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 47] (In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 48] (In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

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

-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 since dehydration reaction due to crosslinking does not occur, it is not easy to cause film shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of the curable resin composition can be effectively suppressed.

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-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) EPICLON (registered trademark) EXA-859CRP (trade name, manufactured by DIC Corporation), EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above trade names, manufactured by ADEKA CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warping and having excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

-Oxycyclobutane compounds (compounds having an oxycyclobutyl group)- As oxycyclobutane compounds, compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester, etc. can be cited. 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 may be used alone or in combination of two or more.

-Benzotriazole compounds (compounds having polybenzotriazole groups)- 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, thereby reducing thermal shrinkage and suppressing the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone (the above trade names, manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

When a polymerizable compound is contained, its content is preferably greater than 0 mass % and less than 60 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5 mass %. The upper limit is more preferably 50 mass % or less, and more preferably 30 mass % or less. In addition, the curable resin composition of the present invention can also be set to a state that substantially does not contain a polymerizable compound. In this state, for example, the content of the polymerizable compound is preferably 0 to 5 mass %, more preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass % relative to the total solid content of the curable resin composition of the present invention. In addition, the above content can also be 0 mass %.

The polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

<Solvent> The curable 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, aromatic hydrocarbons, sulfones, and amides.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (for example, methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (for example, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (for example, methyl 3-alkoxy propionate, ethyl 3-alkoxy propionate, etc. (for example, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-methoxy propionate, etc.) 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. can be cited as preferred ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferred.

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

As the sulfoxides, for example, 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 and the like.

Regarding the solvent, from the viewpoint of improving the properties of the coated surface, a mixture of two or more solvents is also preferred.

In the present invention, one solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl solvent 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. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously.

Regarding the content of the solvent, from the viewpoint of coating properties, the total solid content concentration of the curable resin composition of the present invention is preferably 5 to 80 mass %, 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 desired thickness and coating method.

The solvent may be contained in one kind or in 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.

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

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

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

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds 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 compounds 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.

As specific examples of the migration inhibitor, the following compounds can be cited.

[Chemical formula 49]

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

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

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

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, oligol, p-tert-butyl-oligol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenyl Naphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Chemical formula 50]

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

The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used, the total amount thereof is preferably within the above range.

<Metal Adhesion Improver> The curable 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 the metal adhesion improver include silane coupling agents and the like.

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 51]

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open 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 heterocyclic polymer precursor. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total is within the above range.

<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed within the scope that does not impair the effects of the present invention, such as thermal acid generators, sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are formulated, it is preferred that the total amount thereof be set to 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. As a sensitizer, a sensitizer such as N-phenyldiethanolamine can be cited. In addition, a sensitizing pigment can also be used as a sensitizer. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

When the curable 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 curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent] The curable 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 Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a group of compounds having SH, PH, SiH and GeH in the molecule is used. These compounds generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

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

When the curable 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 curable resin composition of the present invention. The chain transfer agent may be only one or two or more. When there are two or more chain transfer agents, the total amount thereof is preferably within the above range.

[Surfactant] From the viewpoint of further improving the coating properties, various surfactants can be added to the curable 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 (molar %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 52] Furthermore, the surfactant may also include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

When the curable 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 curable 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, the total amount thereof is preferably within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to the curable resin composition of the present invention and the derivatives are concentrated on the surface of the curable resin composition during the drying process after coating.

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

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one type or may be two or more types. When there are two or more types of higher fatty acid derivatives, 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 curable 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 %.

From the viewpoint of insulation, the metal content of the hardening 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 a plurality of metals are included, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities accidentally contained in the hardening 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 hardening resin composition of the present invention, filtering the raw material constituting the hardening 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 view of the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the curable resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the content of halogen atoms in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges, respectively.

As a container for storing the curable 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 curable resin composition, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resin or a bottle having a seven-layer structure of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Preparation of curable resin composition> The curable 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 performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as dust or particles in the curable resin composition, it is preferred to perform filtering using a filter. Preferably, the pore size of the filter is 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. Preferably, the material of the filter is polytetrafluoroethylene, polyethylene or nylon. The filter can be used after being pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a cycle filtration. Furthermore, filtering can be performed after pressurization. When filtering is performed after pressurization, the pressure of pressurization is preferably 0.05MPa or more and 0.3MPa or less. In addition to filtering using a filter, impurity removal treatment using an adsorbent can also be performed. Filtering using a filter and impurity removal treatment using an adsorbent can also be combined. As an 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.

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

(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 described.

The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more, and can be set to 1 μm or more. Also, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

The cured film of the present invention can be laminated with more than 2 layers, and further laminated with 3 to 7 layers to form a laminate. The laminate of the present invention includes more than 2 layers of cured film, and preferably includes a metal layer between any of the above-mentioned cured films. For example, 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 as a preferred one. The above-mentioned first cured film and the above-mentioned second cured film are both the cured films of the present invention. For example, the above-mentioned first cured film and the above-mentioned second cured film are both films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form 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 sealing films, substrate materials (base films or cover films, interlayer insulating films for flexible printed circuit boards), or insulating films for actual mounting purposes such as those mentioned above that are etched to form patterns. For such applications, for example, reference can be made to Science & Technology Co., Ltd., “Advanced Functionality and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, “Fundamentals and Development of Polyimide Materials”, November 2011, and Japan Polyimide and Aromatic Polymer Research Society, “Latest Polyimide: Fundamentals and Applications”, NTS, August 2010.

Furthermore, the cured film of the present invention can also be used in the production of offset printing plates or screen printing plates, the use of etched parts, the production of protective varnishes and dielectric layers in electronics, especially microelectronics, etc.

The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming process of applying the curable resin composition of the present invention to a substrate to form a 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. Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming process and the above-mentioned development process as needed, and more preferably 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 curable resin composition to a substrate to form a film (curable 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 above heating process, the resin layer cured by exposure can be further cured. In the heating process, for example, the above-mentioned hot alkali generator is decomposed, and sufficient curability can be obtained.

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. The method for manufacturing a laminated body of the present embodiment forms a cured film according to the above-mentioned method for manufacturing a cured film, and then performs process (a) or processes (a) to (c), or processes (a) to (d) again after forming the cured film. 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 formed. In the present invention, it is preferred to provide a metal layer on a portion where a cured film is provided or between the cured films, or in both. In addition, in the manufacture of the laminate, it is not necessary to repeat all of 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) multiple 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 curable resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates of plasma display panels (PDP). In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. In addition, as a substrate, for example, a plate-shaped substrate (substrate) is used.

Furthermore, when a hardening 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 curable resin composition to the base material, coating is preferred.

Specifically, applicable methods include 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 perspective of thickness uniformity of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred, and for 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, a method of transferring a coating film formed by applying the above-mentioned applying method to a pseudo support body in advance can also be applied. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

<Drying process> The manufacturing method of the present invention may further include a drying process for removing the solvent after the film (hardening resin composition layer) is formed and 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 is exemplified as 30 seconds to 20 minutes, 1 to 10 minutes is preferred, and 3 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 (hardening resin composition layer). The exposure amount is not particularly limited as long as it can harden the hardening resin composition. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated as the exposure energy at a wavelength of 365 nm.

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

Regarding the exposure wavelength, if described in terms of its relationship with the light source, the following examples can be cited: (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, etc. The curable resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays. This can provide a particularly high exposure sensitivity.

<Developing process> The manufacturing method of the present invention may include a developing process of developing (developing the above-mentioned film) the exposed film (hardening resin composition layer). By developing, the unexposed part (non-exposed part) is removed. There is no particular limitation on the developing method as long as the desired pattern can be formed. For example, a developing method such as rotary immersion, spraying, immersion, ultrasonic wave, etc. can be used.

Development is performed using a developer. As long as the developer can remove the unexposed portion (non-exposed portion), it can be used without particular limitation. The developer preferably contains an organic solvent, and more preferably contains 90% or more of the organic solvent. 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 as a calculated value by inputting a structural formula into ChemBioDraw.

As for the organic solvent, examples of the esters include preferably 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 ethoxy acetate, 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 propionate)), 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 solvent acetate, ethyl Examples of the solvent include acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and examples of ketones include preferably methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like; and examples of aromatic hydrocarbons include preferably toluene, xylene, anisole, limonene, and the like; and examples of sulfoxides include preferably dimethyl sulfoxide.

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

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

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing process is not particularly limited, but the developing process can usually be performed at 20 to 40°C.

After the treatment with the developer, rinsing can be performed. It is preferred that the rinsing be performed with a solvent different from the developer. For example, the solvent included in the curable resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

<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 base is generated by decomposing the above-mentioned hot alkali generator, and a cyclization reaction of the heterocyclic polymer precursor is carried out. In addition, although the curable resin composition of the present invention may contain a free radical polymerizable compound other than the heterocyclic polymer precursor, the curing of the free radical polymerizable compound other than the unreacted heterocyclic polymer precursor can also be carried out in the process. As the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is further preferred, 150°C or higher is further preferred, 160°C or higher is further preferred, and 170°C or higher is further preferred. As the upper limit, 500°C or lower is preferred, 450°C or lower is more preferred, 350°C or lower is further preferred, 250°C or lower is further preferred, and 220°C or lower is further preferred.

Regarding heating, it is preferred that the heating rate be 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 volatile amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated.

The temperature at the start of heating is preferably 20°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 curable resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable 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 forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is not yet clear, but it is believed that this is because the acetylene groups of the heterocyclic polymer precursor between the layers undergo cross-linking reactions.

Heating can be performed in stages. For example, the pre-treatment process can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pre-treatment 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. The properties of the membrane can be improved by such pre-treatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a process of two or more stages, for example, pretreatment process 1 can be carried out in the range of 100 to 150°C, and then pretreatment process 2 can be carried out in the range of 150 to 200°C.

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

Regarding the heating process, it is preferred to conduct the process in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon to prevent the decomposition of the heterocyclic polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer forming process> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the film (hardening 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 and aluminum 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 Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and a combination of 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 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest wall portion.

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

The lamination process includes a series of processes including (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, and (d) a heating process, which are performed again in sequence on the surface of the hardened film (resin layer) or the metal layer. Among them, it is possible to have a mode in which only the film forming process (a) is repeated. In addition, it is also possible to have a mode in which the heating process (d) is performed at the end or in the middle of the lamination. That is, it is also possible to have a mode in which the processes (a) to (c) are repeated a specified number of times, and then the heating (d) is performed, thereby hardening the hardening resin composition layer to be laminated. Furthermore, the (c) developing process may include the (e) metal layer forming process, and the heating in (d) may be performed each time, or may be performed collectively after a predetermined number of layering processes. It is beyond doubt that the layering process may also appropriately include the above-mentioned drying process and heating process.

When the lamination process is further performed after the lamination 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. Plasma treatment is exemplified as the surface activation treatment.

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

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, etc., in which the number of resin layers is 3 or more and 7 or less is preferred, and a structure of 3 or more and 5 or less 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 hardening resin composition in a manner covering the metal layer. Specifically, it is possible to cite an embodiment in which (a) a film forming process, (b) an exposure process, (c) a developing process, (e) a metal layer forming process, and (d) a heating process are sequentially repeated, or an embodiment in which (a) a film forming process, (b) an exposure process, (c) a developing process, and (e) a metal layer forming process are sequentially repeated, and (d) a heating process is provided at the end or in the middle. By alternately performing the lamination process of the hardening resin composition layer (resin layer) and the metal layer forming process, the hardening resin composition layer (resin layer) and the metal layer can be alternately laminated.

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 using the curable resin composition of the present invention in the formation of 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, and such contents are incorporated into this specification. [Example]

The present invention is further described in detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate 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 based on mass.

<Synthesis Example 1> [Synthesis of a polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol (A-1: a polyimide precursor having no free radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while the temperature was maintained at -10±4°C. The viscosity increased during the addition of SOCl _2. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes while maintaining the temperature at -5 to 0°C. Next, after the reaction mixture was reacted at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical Formula 53]

<Synthesis Example 2> [Synthesis of a polyimide precursor derived from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: a polyimide precursor having a radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic acid dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. [Chemical Formula 54]

<Synthesis Example 3> [Synthesis of a polyimide precursor (A-3: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical Formula 55]

<Synthesis Example 4> [Synthesis of a polyimide precursor (A-4: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (o-tolidine) and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. [Chemical Formula 56]

<Synthesis Example 5> [Synthesis of polybenzoxazole precursor (A-5) derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydiphenylformyl chloride] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone and stirred to dissolve. Then, 11.21 g of 4,4'-oxydiphenylformyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, 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. The weight average molecular weight of the polybenzoxazole precursor was 15,000. [Chemical Formula 57]

<Synthesis Example 6> [Synthesis of a polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-6: a polyimide precursor having a free radical polymerizable group)] 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a separation flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction was terminated, the mixture was cooled to room temperature and then left to stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour. Thereafter, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A-6. The weight average molecular weight (Mw) of the polymer A-6 was measured to be 20,000.

<Synthesis Example 7> [Synthesis of a polyimide precursor derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-7: a polyimide precursor having a free radical polymerizable group)] In Synthesis Example 6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride, a polymer A-7 was obtained by reacting in the same manner as described in Synthesis Example 6. The weight average molecular weight (Mw) of the polymer A-7 was measured to be 22,000.

<Synthesis Example 8> [Synthesis of Compound B-1] Add 450 g of methanol, 15 g of tryptic mercaptan (manufactured by TCI), and 25.3 g of triethylamine to a three-necked flask and dissolve them completely. Then, while cooling with ice, 30.5 g of p-chloromethylstyrene (manufactured by AGC SEIMI CHEMICAL CO., LTD.) dissolved in 50 g of methanol was added dropwise over 20 minutes. After the addition was completed, the mixture was stirred for 4 hours while cooling with ice (crystals precipitated in the reaction solution). The reaction solution was added to 1,000 g of pure water, stirred at room temperature for 30 minutes, and the crystals were filtered out. The obtained crude crystals were re-slurried in 300 g of methanol and 100 g of ethyl acetate, and dried under vacuum to obtain 11.5 g of B-1 (yield 30%).

[Synthesis of Compound B-5 and Compound B-12] Compounds B-5 and B-12 were synthesized by the same method as the synthesis of Compound B-1 except that the synthesis raw materials were appropriately changed. The structures of Compounds B-5 and B-12 are shown in the following formula (B-5) or formula (B-12), respectively.

[Chemical formula 58]

<Examples and Comparative Examples> In each example, the components listed in Table 1 or Table 2 below were mixed to obtain each hardening resin composition. In addition, in each comparative example, the components listed in Table 1 or Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the components listed in the columns other than "Solvent" in Table 1 or Table 2 is set to the amount listed in "Parts by Mass" in Table 1, and the content of the components listed in the "Solvent" column in Table 1 or Table 2 is set to the amount at which the solid content concentration of the composition becomes the value listed in Table 1 or Table 2. For example, the description of "I-1/I-2" and "80/20" in "Solvent" in Table 1 or Table 2 indicates that the content ratio of I-1 to I-2 is I-1:I-2=80:20 in terms of mass ratio. The obtained curable resin composition and the comparative composition were pressure filtered through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Table 1 or Table 2, the description of "-" indicates that the composition does not contain the component.

[Table 1] Embodiment 1 2 3 4 5 6 7 8 9 10 11 12 13 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 Polymer precursor Type A-3 A-3 A-3 A-1 A-2 A-4 A-5 A-3 A-3 A-3 A-3 A-3 A-3 Quality 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 The compound represented by formula (1-1) Type B-1 B-5 B-12 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 6.06 Polymeric compounds Type - - - - - - - - - - - - C-1 Quality - - - - - - - - - - - - 6.06 Additives Type - - - - - - - - - - - - - Quality - - - - - - - - - - - - - Photopolymerization initiator Type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-1 D-1 D-1 D-1 D-1 Quality 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 Onium salt or hot alkali generator Type E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-2 E-1 E-1 E-1 E-1 Quality 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 Polymerization inhibitor Type F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 Quality 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 Migration inhibitors Type G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-2 G-1 G-1 Quality 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 Metal Adhesion Improver Type H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-2 H-1 Quality 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 Solvent Type I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 Quality Ratio 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 Evaluation results Drug resistance A A B A A A A A A A A A B

[Table 2] Embodiment Comparison Example 14 15 16 1 Solid content concentration (mass %) 42 42 40 42 Polymer precursor Type A-3 A-3 A-6 /A-7 A-6 /A-7 Quality 80.74 80.74 43 /43 43 /43 The compound represented by formula (1-1) Type B-1 B-1 B-1 - Quality 6.06 6.06 3.75 - Polymeric compounds Type C-2 C-3 C-1 C-1 Quality 6.06 6.06 3 6.75 Additives Type - - J-1 J-1 Quality - - 3.5 3.5 Photopolymerization initiator Type D-1 D-1 D-1 D-1 Quality 2.83 2.83 1.75 1.75 Onium salt or hot alkali generator Type E-1 E-1 - - Quality 2.26 2.26 - - Polymerization inhibitor Type F-1 F-1 F-3 F-3 Quality 0.16 0.16 0.05 0.05 Migration inhibitors Type G-1 G-1 - - Quality 0.28 0.28 - - Metal Adhesion Improver Type H-1 H-1 H-2 /H-3 H-2 /H-3 Quality 1.61 1.61 0.5 /0.5 0.5 /0.5 Solvent Type I-1 /I-2 I-1 /I-2 I-3 /I-4 I-3 /I-4 Quality Ratio 80/20 80/20 80/20 80/20 Evaluation results Drug resistance B B A C

The details of each component listed in Table 1 or Table 2 are as follows.

[Polymer precursor] ・A-1 to A-7: A-1 to A-7 synthesized above

[Specific polymerizable compounds] ・B-1, B-5 and B-12: B-1, B-5 and B-12 synthesized above

[Polymerizable compound] ・C-1 to C-3: Compounds having the following structure [Chemical formula 59]

[Additives] ・J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Photopolymerization initiator] ・D-1 and D-2: Compounds having the following structure [Chemical formula 60]

[Thermoalkali generator] ・E-1~E-2: Compounds with the following structure [Chemical formula 61]

[Polymerization inhibitor] ・F-1 to F-2: Compounds of the following structures ・F-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical formula 62]

[Migration inhibitor] ・G-1 to G-2: Compounds with the following structure [Chemical formula 63] [Metal Adhesion Improver] ・H-1 to H-3: Compounds with the following structures [Chemical Formula 64]

[Solvent] ・I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) ・I-2: Dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) ・I-3: N-methyl-2-pyrrolidone (manufactured by Ashland Co., Ltd.) ・I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Production of Cured Film> In each of the Examples and Comparative Examples, a curable resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer with the resin layer formed thereon was dried on a heating plate at 100°C for 4 minutes to form a resin composition layer with a uniform thickness of 20 μm on the silicon wafer. The resin composition layer on the silicon wafer was exposed with an exposure energy of 400 mJ/ ^cm2 using a wideband exposure machine (UX-1000SN-EH01 manufactured by USHIO INC.), and the exposed resin composition layer was heated at a rate of 5°C/min in a nitrogen atmosphere until it reached 180°C, and then heated at that temperature for 2 hours. The heated resin composition layer and the silicon wafer were immersed in a 3% by mass hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled heated resin composition layer was used as a cured film.

<Evaluation> In each embodiment and comparative example, the obtained cured film was evaluated for chemical resistance, elongation at break, and resolution. The following describes the details of the evaluation method in each evaluation.

[Chemical resistance] The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical: A mixture of 90:10 (mass ratio) of dimethyl sulfoxide (DMSO) and 25 mass % tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The cured film 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 film thickness was measured at 10 locations on the coated surface using an ellipsometer (KT-22 manufactured by Foothill Co., Ltd.), and the film thickness was calculated as the arithmetic mean. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in Table 1 or Table 2. It can be said that the smaller the dissolution rate value, the better the chemical resistance of the cured film.

-Evaluation criteria- A: Dissolution rate is less than 250nm/min. B: Dissolution rate is more than 250nm/min and less than 500nm/min. C: Dissolution rate is more than 500nm/min.

From the above results, it can be seen that the cured film obtained by the curable resin composition containing the heterocyclic polymer precursor and the compound represented by formula (1-1) of the present invention has excellent chemical resistance. The curable resin composition of Comparative Example 1 does not contain the compound represented by formula (1-1). It can be seen that the cured film obtained by the curable resin composition of Comparative Example 1 has poor chemical resistance.

<Example 101> The curable resin composition used in Example 1 was applied to the surface of the resin substrate on which the copper thin layer was formed by spin coating, and dried at 100°C for 5 minutes to form a curable resin composition layer with a film thickness of 20μm, and then exposed using a stepper (Nikon Corporation, 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, the layer pattern was obtained by developing with cyclopentanone for 30 seconds and rinsing with PGMEA for 20 seconds. Then, the layer was heated at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. The insulation properties of the interlayer insulating film for the redistribution layer are excellent. In addition, the semiconductor device was manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without

without

Claims (21)

A hardening resin composition comprising: a pre-driver selected from polyimide and benzo

At least one polymer precursor from the group of azole precursors; a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule; and a photo-radical polymerization initiator, wherein the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is a compound represented by the following formula (1-1),

In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, a heterocyclic group, and groups bonded to 2 or more of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom, and m represents an integer of 2 to 6. A curable resin composition comprises: a polyimide precursor having a repeating unit represented by the following formula (1); and a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule, represented by the following formula (1-1),

In formula (1), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 contains a free radical polymerizable group,

In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, a heterocyclic group, and groups bonded to 2 or more of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom, and m represents an integer of 2 to 6. A curable resin composition is used to form an interlayer insulating film for a redistribution layer. The curable resin composition comprises: a polyimide precursor and a benzophenone

At least one polymer precursor in the group of azole precursors; and a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule, wherein the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is a compound represented by the following formula (1-1),

In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, a heterocyclic group, and groups bonded to 2 or more of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom, and m represents an integer of 2 to 6. A hardening resin composition comprising: a pre-driver selected from polyimide and benzo

At least one polymer precursor in the group of azole precursors; and a compound having two or more aromatic rings directly bonded to vinyl groups which may be substituted in the molecule, wherein the compound having two or more aromatic rings directly bonded to vinyl groups which may be substituted in the molecule is a compound represented by the following formula (1-1), and the ratio of ^sp3 carbon to the number of all atoms excluding hydrogen atoms in Z in the compound having two or more aromatic rings directly bonded to vinyl groups which may be substituted in the molecule is 0.2 to 0.4,

In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of 2 or more, an unsaturated aliphatic alkyl group having a valence of 2 or more, a cycloalkyl group, -O-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, a heterocyclic group, and groups bonded to 2 or more of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, ^R1s each independently represent a hydrogen atom, and m represents an integer of 2 to 6. A hardening resin composition comprising: a pre-driver selected from polyimide and benzo

At least one polymer precursor in the group of azole precursors; and a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule, wherein the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is a compound represented by the following formula (1-1),

In formula (1-1), Z is a group represented by the following formula (Z-2), ^R1 represents a hydrogen atom, m is 3,

In formula (Z-2), A2 represents a alkyl group or a heterocyclic group, ^LZ3 to ^LZ5 each independently represent a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, a alkylene group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a heterocyclic group, and groups bonded to two or more groups, ^RA represents a hydrogen atom, an alkyl group, or an aryl group. When there are plural ^RAs , the plural ^RAs may be the same or different, and * each independently represents a bonding site to the benzene ring in formula (1-1). A hardening resin composition comprising: a pre-driver selected from polyimide and benzo

At least one polymer precursor in the group of azole precursors; and a compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule, wherein the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is a compound represented by the following formula (1-1),

In formula (1-1), Z is an m-valent linking group selected from the group consisting of a saturated aliphatic alkyl group having a valence of more than 2, an unsaturated aliphatic alkyl group having a valence of more than 2, a cycloalkyl group, -O-, -S-, -N( ^RA )-, -C(=O)-O-, -C( ^RA )=N-, -C(=O)-, -S(=O) _2- , a heterocyclic group, and groups bonded to more than two of these groups, ^RA is a hydrogen atom, an alkyl group, or an aryl group. When ^RA exists in a plurality, the plurality of ^RAs may be the same or different, ^R1 each independently represents a hydrogen atom, m represents an integer of 2 to 6, and the aforementioned Z comprises a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isobutyl ring, a tetrazole ...

Azole

Azole

oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzo

Azole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, tantalum

Ring, pyrimidine ring, pyridine

Ring, three

Ring, quinoline ring, quinoline

As the heterocyclic ring in the heterocyclic group, at least one heterocyclic ring selected from the group consisting of a phenoxy ring, a furan ring and a thiophene ring is used. The curable resin composition as claimed in any one of claims 1 to 5, wherein the aforementioned Z comprises a ring selected from a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isocyanate ring,

Azole

Azole

oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzo

Azole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, tantalum

Ring, pyrimidine ring, pyridine

Ring, three

Ring, quinoline ring, quinoline

As the heterocyclic ring in the heterocyclic group, at least one heterocyclic ring selected from the group consisting of a phenoxy ring, a furan ring and a thiophene ring is used. The curable resin composition as described in any one of claim 1 to claim 3, claim 5 and claim 6, wherein the ratio of the number of ^sp3 carbons to the number of all atoms excluding the hydrogen atoms in Z in the compound having two or more aromatic rings directly bonded to vinyl groups which may be substituted in the molecule is 0.2-0.4. The curable resin composition as described in any one of claim 2 to claim 6 further comprises a photo-radical polymerization initiator. The curable resin composition as described in any one of claim 1, claim 3 to claim 6 comprises a polyimide precursor as the aforementioned polymer precursor. The curable resin composition as claimed in claim 10, wherein the polyimide precursor has a repeating unit represented by the following formula (1):

In formula (1), ^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 hardening resin composition as described in claim 11, wherein at least one of R ¹¹³ and R ¹¹⁴ in the above formula (1) contains a free radical polymerizable group. The curable resin composition as described in any one of claim 1, claim 2, claim 4 to claim 6 is used to form an interlayer insulating film for a redistribution layer. A curable resin composition as described in any one of claim 1 to claim 6, wherein the molecular weight of the compound having two or more aromatic rings directly bonded by substituted vinyl groups in the molecule is 200 to 2,000. The hardening resin composition as described in any one of claim 1 to claim 6 further comprises an onium salt. A cured film formed by curing the curable resin composition described in any one of claim 1 to claim 15. A laminate comprising two or more layers of the hardened films described in claim 16, wherein a metal layer is included between any of the hardened films. A method for manufacturing a cured film, comprising a film forming process in which a curable resin composition described in any one of claim 1 to claim 15 is applied to a substrate to form a film. The method for manufacturing a hardened film as described in claim 18 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 18 or claim 19 includes a heating process of heating the aforementioned film at 50°C to 450°C. A semiconductor device comprises the hardened film of claim 16 or the laminate of claim 17.