TWI875941B - Resin composition, cured film, laminate, method for producing cured film, and semiconductor element - Google Patents

Abstract

The present invention provides a resin composition, a cured film formed by curing the 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 resin composition includes at least one resin selected from the group consisting of polyimide and a polyimide precursor, and includes a structure represented by formula (1-1) in a solid component.

Description

Resin composition, cured film, laminate, method for producing cured film, and semiconductor element

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

Polyimide is suitable for various applications due to its excellent heat resistance and insulation properties. The above applications are not particularly limited, but for example, for semiconductor components to be mounted, it can be used as an insulating film or sealing material or a protective film. It is also used as a base film or coverlay film for flexible substrates.

For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing polyimide itself or a resin composition containing a precursor of polyimide (also referred to as "polyimide precursor"). Such a resin composition is applied to a substrate, for example, by coating, and then exposed, developed, heated, etc. as needed, so that a hardened resin can be formed on the substrate. Since the resin composition can be applied by a known coating method, it can be said that the adaptability in manufacturing is excellent, for example, the design freedom of the shape, size, application position, etc. of the applied resin composition is high. In addition to the high performance of polyimide, from the perspective of excellent manufacturing adaptability, the industrial application development of resin compositions containing polyimide or polyimide precursors is increasingly expected.

For example, Patent Document 1 discloses a negative photosensitive resin composition comprising 100 parts by mass of a polyimide precursor having a specific structural unit, 1 to 20 parts by mass of a photopolymerization initiator (B), and 0.1 to 30 parts by mass of at least one compound or polymer selected from the group consisting of (C) a compound or polymer having a specific structure and (D) a compound or polymer having a specific structure.

[Patent Document 1] Japanese Patent Application Publication No. 2011-059656

The following step is performed, that is, a cured film is formed on a metal layer using a resin composition containing at least one resin selected from a group including polyimide and a polyimide precursor. In such a use, it is desirable to provide a resin composition having excellent adhesion between the cured film and the metal.

The object of the present invention is to provide a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor element including the cured film or the laminate, wherein the resin composition can obtain a cured film having excellent adhesion to metal.

Representative embodiments of the present invention are shown below. <1> A resin composition comprising at least one resin selected from the group consisting of polyimide and polyimide precursor, wherein the solid component comprises a structure represented by formula (1-1). [Chemical Formula 1] In formula (1-1), ^R1 and ^R2 each independently represent an aliphatic group or an aromatic group, the carbon atom or the hydrocarbon group of the aliphatic group or the aromatic group may be substituted by a heteroatom, ^X1 represents an oxygen atom or a sulfur atom, ^L1 represents -C(=O)- or -S(=O) _2- , * ¹ and * ² each independently represent a bonding site with another structure, and at least two of ^R1 , ^R2 , the structure bonded to * ¹ and the structure bonded to * ² may bond to form a ring structure. <2> The resin composition as described in <1>, wherein the resin comprises the structure represented by formula (1-1). <3> The resin composition as described in <1> or <2>, further comprising a compound that is a compound having a structure represented by the above formula (1-1) and is different from the above resin. <4> The resin composition as described in any one of <1> to <3>, comprising a structure represented by the following formula (1-2) as the structure represented by the above formula (1-1). [Chemical Formula 2] In formula (1-2), R ²¹ and R ²² each independently represent an aliphatic group or an aromatic group, the carbon atom or the hydrocarbon group of the aliphatic group or the aromatic group may be substituted by a heteroatom, R ²³ represents a hydrogen atom or a monovalent organic group, * represents a bonding site with another structure, and at least two of R ²¹ , R ²² , R ²³ and the structure bonded to * may bond to form a ring structure. <5> The resin composition as described in any one of <1> to <4>, wherein the molar amount of the structure represented by the above formula (1-1) is 0.01 to 1.0 mmol/g relative to the total solid content of the resin composition. <6> The resin composition as described in any one of <1> to <5>, further comprising a photopolymerization initiator. <7> A resin composition as described in any one of <1> to <6>, further comprising a crosslinking agent. <8> A resin composition as described in any one of <1> to <7>, which is used to form an interlayer insulating film for a redistribution layer. <9> A cured film, which is formed by curing the resin composition as described in any one of <1> to <8>. <10> A laminate having two or more layers of the cured films as described in <9>, and having a metal layer between any of the cured films. <11> A method for producing a cured film, which includes a film forming step, in which the resin composition as described in any one of <1> to <8> is applied to a substrate to form a film. <12> A method for producing a cured film as described in <11>, comprising heating the film at 50 to 450°C. <13> A semiconductor device having the cured film described in <9> or the laminated body described in <10>. [Effects of the invention]

According to the present invention, a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor element including the cured film or the laminate can be provided. The resin composition can obtain a cured film having excellent adhesion to metal.

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 "～" refers to the range including the numerical values recorded before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only indicates an independent step, but also includes steps that cannot be clearly distinguished from other steps as long as the expected effect of the step 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, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as 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 rays), 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 refers to the total mass of all components of the composition excluding the solvent. 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 the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and using guard 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 a washing liquid. In addition, unless otherwise specified, the detection in the GPC measurement is the detection using a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", it is sufficient as long as there are other layers on the upper side or lower side of the layer serving as a reference among the plurality of layers concerned. In other words, a third layer or a third element may be further interposed between the layer serving as a reference and the other layers mentioned above, and the layer serving as a reference and the other layers mentioned above do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "upper", or, in the case of a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "upper", and the opposite direction is referred to as "lower". In addition, the setting of the up and down directions is for the convenience of explaining this manual. In actual forms, the "up" direction in this manual may also be different from the vertical direction. In this manual, unless otherwise stated, in a composition, each component contained in the composition may include two or more compounds corresponding to the component. In addition, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to the component. In this manual, unless otherwise stated, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this manual, the combination of the best form is the best form.

(Resin composition) The resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention") contains at least one resin selected from the group consisting of polyimide and polyimide precursors, and contains the structure represented by formula (1-1) in the solid component. Hereinafter, at least one resin selected from the group consisting of polyimide and polyimide precursors is also referred to as "specific resin".

[Chemical formula 3] In formula (1-1), ^R1 and ^R2 each independently represent an aliphatic group or an aromatic group, the carbon atom or the hydrocarbon group of the aliphatic group or the aromatic group may be substituted by a heteroatom, ^X1 represents an oxygen atom or a sulfur atom, ^L1 represents -C(=O)- or -S(=O) _2- , * ¹ and * ² each independently represent a bonding site with other structures, and at least ^two of ^R1 , ^R2 , the structure bonded to * ¹ and the structure bonded to *2 may bond to form a ring structure.

The following step is performed, that is, a cured film is formed on the metal layer using a resin composition containing at least one resin selected from the group including polyimide and a polyimide precursor. The above-mentioned cured film is used for various components, for example, as an insulating film, a sealing material, a protective film, a base film of a flexible substrate, a cover film, etc. In such a cured film formed on the metal layer, it is required that the cured film is not easily peeled off from the metal layer, that is, the metal layer and the cured film have excellent adhesion. As a result of in-depth research, the inventors found that in the above-mentioned resin composition, by including the structure represented by formula (1-1) in the solid component, the adhesion between the metal layer and the cured film can be improved. Although the mechanism by which the above effect can be obtained is not clear, it is speculated that this is because the structure contained in the cured film formed by the above resin composition interacts with the metal contained in the metal layer. In addition, it is believed that due to the above interaction, according to the resin composition of the present invention, even when the above cured film and the above metal layer are heated (for example, heated at 175°C for 1,000 hours), the adhesion between the cured film and the metal layer is excellent.

Among them, in Patent Document 1, there is no description or suggestion of a resin composition containing the structure represented by Formula (1-1) in the solid component. The resin composition of the present invention is described in detail below.

<Structure represented by formula (1-1)> The structure represented by formula (1-1) only needs to be included in the solid component of the resin composition. For example, the structure represented by formula (1-1) can be included in the structure of a specific resin. The resin composition can be a compound containing the structure represented by the above formula (1-1) and a compound different from the above resin (hereinafter, also referred to as a "specific compound"). In addition, the resin composition contains a resin having a structure represented by formula (1-1) and can contain a specific compound.

[R ¹ and R ² ] In formula (1-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group, preferably an aliphatic alkyl group or an aromatic alkyl group, and more preferably an aliphatic alkyl group. As the aliphatic alkyl group, a saturated aliphatic alkyl group having 1 to 20 carbon atoms is preferred, a saturated aliphatic alkyl group having 3 to 10 carbon atoms is more preferred, a saturated aliphatic alkyl group having 3 to 6 carbon atoms is further preferred, and an isopropyl group or a cyclohexyl group is further preferred. The aliphatic alkyl group may have a known substituent, but having no substituent is also one of the preferred aspects of the present invention. As the aromatic alkyl group, an aromatic alkyl group having 6 to 20 carbon atoms is preferred, more preferably a phenyl group or a naphthyl group, and further preferably a phenyl group. The above aromatic alkyl group may have a known substituent, and an alkyl group may be cited as the substituent. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms is more preferred, a branched alkyl group having 3 to 6 carbon atoms is further preferred, and an isopropyl group is particularly preferred. The number of the above substituents is not particularly limited, but 1 to 5 is preferred, 1 to 3 is more preferred, and 2 is further preferred. In addition, the carbon atoms or alkyl groups of the aliphatic group or aromatic group in ^R1 and ^R2 may be substituted by heteroatoms. As heteroatoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc. may be cited. Specifically, structures such as -O-, -NR ^N -, -N=, and -S- may be contained inside the aliphatic group or aromatic group. The above-mentioned ^RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[X ¹ ] In the formula (1-1), X ¹ represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred.

[L ¹ ] In the formula (1-1), L ¹ represents -C(=O)- or -S(=O) ₂ -, and -C(=O)- is preferred.

[Ring structure] In formula (1-1), at least two of R ¹ , R ² , the structure bonded to * ¹ and the structure bonded to * ² may bond to form a ring structure. Examples of the ring structure to be formed include a hydantoin ring and an N-acyl imidazolidinone ring, but the ring structure is not limited thereto. In the present invention, an aspect in which any one of R ¹ , R ² , the structure bonded to * ¹ and the structure bonded to * ² does not form a ring structure is also one of the preferred aspects.

<Structure represented by Formula (1-2)> The resin composition of the present invention preferably contains the structure represented by the following Formula (1-2) as the structure represented by Formula (1-1). [Chemical Formula 4] In formula (1-2), R ²¹ and R ²² each independently represent an aliphatic group or an aromatic group, the carbon atom or the hydrocarbon group of the aliphatic group or the aromatic group may be substituted by a heteroatom, R ²³ represents a hydrogen atom or a monovalent organic group, * represents a bonding site with other structures, and at least two of R ²¹ , R ²² , R ²³ and the structure bonded to * may bond to form a ring structure.

[R ²¹ and R ²² ] In the formula (1-2), R ²¹ and R ²² have the same meanings as R ¹ and R ² in the formula (1-1), respectively, and preferred embodiments thereof are also the same.

[R ²³ ] In formula (1-2), R ²³ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Examples of the aliphatic hydrocarbon group or the aromatic hydrocarbon group include the aliphatic hydrocarbon group or the aromatic hydrocarbon group mentioned above for R ¹ , and the preferred embodiments are the same.

[Ring structure] In formula (1-2), at least two of R ²¹ , R ²² , R ²³ and the structure bonded to * may bond to form a ring structure. Examples of the ring structure to be formed include a hydantoin ring, an N-acyl imidazolidinone ring, etc., but the ring structure is not limited thereto. In the present invention, an aspect in which any of R ²¹ , R ²² , R ²³ and the structure bonded to * does not form a ring structure is also one of the preferred aspects.

[Content] From the viewpoint of improving adhesion, the molar content of the structure represented by formula (1-1) relative to the total solid content of the resin composition is preferably 0.01 to 1.0 mmol/g, more preferably 0.01 to 0.85 mmol/g, and even more preferably 0.015 to 0.75 mmol/g. It is believed that as long as the molar content is below the lower limit, a cured film with excellent adhesion to metal can be easily obtained. In addition, it is believed that as long as the molar content is below the upper limit, a cured film with excellent storage stability of the composition, such as inhibiting cyclization of the polyimide precursor and inhibiting the scission of the main chain of the specific resin, can be easily obtained. There is no particular limitation on the method for measuring the above content, but for example, the measuring method in the embodiment described below can be cited. There is no particular limitation on the method for measuring the above total solid content, but for example, the measuring method in the embodiment described below can be cited, and a method of setting the temperature and air pressure and drying while confirming that the resin composition has no volatile components other than the solvent can be cited. However, as a method for measuring the total solid content, as long as it is a method that can determine the content of components other than the solvent in the resin composition as the total solid content, it is not limited to this. The above content is the molar amount of the structure represented by formula (1-1) relative to the total solid content of the resin composition. For example, when the resin composition contains a resin having a structure represented by formula (1-1) and contains a specific compound, the total amount of the structure represented by formula (1-1) contained in the resin and the structure represented by formula (1-1) contained in the specific compound is preferably within the above range.

<Resin> The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide and polyimide precursor. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. In addition, the specific resin preferably has a free radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition preferably contains the radical polymerization initiator described below as a polymerization initiator, more preferably contains the radical polymerization initiator described below as a photosensitizer and contains the radical crosslinking agent described below, and further preferably contains the radical polymerization initiator described below as a polymerization initiator, contains the radical crosslinking agent described below, and contains the sensitizer described below. Such a resin composition, for example, forms a negative photosensitive layer. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains the photoacid generator described below. Such a resin composition can form, for example, a chemically amplified positive photosensitive layer or a negative photosensitive layer.

Furthermore, the specific resin preferably contains a structure represented by formula (1-1). The preferred embodiment of the structure represented by formula (1-1) is as described above. When the specific resin contains a structure represented by formula (1-1), the specific resin may have the structure represented by formula (1-1) in the main chain, but preferably has it in the side chain. In this specification, "main chain" refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" refers to other bond chains. When the specific resin contains the structure represented by formula (1-1), it is preferred that the specific resin contains a repeating unit represented by formula (2-1) described later or contains a structure represented by formula (2-2) described later at the terminal. In addition, the resin composition may include a specific resin containing the structure represented by formula (1-1) and a specific resin not containing the structure represented by formula (1-1).

[Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but preferably comprises a repeating unit represented by the following formula (2). [Chemical Formula 5] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

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

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferred, and a diamine containing a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of aromatic groups include the following.

[Chemical formula 6] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, at least one diamine selected from the following can be cited: 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine. ; m- or p-phenylenediamine, diaminotoluene, 4,4’- or 3,3’-diaminobiphenyl, 4,4’-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4’- and 3,3’-diaminodiphenylmethane, 4,4’- and 3,3’-diaminodiphenyl sulfide, 4,4’- and 3,3’-diaminodiphenyl sulfide, 4,4’- or 3,3’-diaminobenzophenone, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 2,2-diaminodiphenyl (4-aminophenyl) propane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) propane, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) propane, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide 、Bis[4-(3-aminophenoxy)phenyl]sulfone、Bis[4-(2-aminophenoxy)phenyl]sulfone、1,4-bis(4-aminophenoxy)benzene、9,10-bis(4-aminophenyl)anthracene、3,3'-dimethyl-4,4'-diaminodiphenylsulfone、1,3-bis(4-aminophenoxy)benzene、1,3-bis(3-aminophenoxy)benzene、1,3-bis(4-aminophenyl)benzene、3,3'-diethyl-4,4'-diaminodiphenylmethane、3,3'-dimethyl-4,4'-diaminodiphenylmethane、4,4'-diaminooctafluorobiphenyl、2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Aminodiphenylmethane, 2,4- and 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, ethylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) )biphenyl, 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)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’-hexafluorotriphenylmethane and 4,4’-diaminotetraphenyl.

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

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

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

Furthermore, from the viewpoint of the i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of the i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 7] In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 8] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds that provide the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical Formula 9]

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

Formula (6) [Chemical formula 11]

Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing the anhydride 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 represented by the following formula (O). Formula (O) [Chemical Formula 12] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

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

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

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

[Chemical formula 13]

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

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

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be any of a linear, branched, and cyclic group. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy). The cyclic alkyl group may be a monocyclic or polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of both high sensitivity and stability. Furthermore, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group specifically includes a substituted or unsubstituted benzene ring, a naphthyl ring, a pentadiene ring, an indene ring, an azulene ring, a heptadiene ring, an indenyl ring, a perylene ring, a condensed pentadiene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed benzene ring, a chrysene ring, a tert-butylbenzene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, Indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinolyl ring, naphthidine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthidine ring, acridine ring, phenanthroline ring, thianthion ring, chromene ring, phenanthroline ring, phenanthrene ring, phenanthrene ring, phenanthrene ring, phenanthrene ring or phenanthrene ring. Benzene ring is the most preferred.

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

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and an acetal group is more preferred from the viewpoint of exposure sensitivity. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, and the like. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

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

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

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the width of the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 14] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2) respectively, and their preferred ranges are also the same. R ¹¹² has the same meanings as R ¹¹² in formula (5), and its preferred ranges are also the same.

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

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

Furthermore, when the polyimide precursor has a structure represented by formula (1-1), it is preferred that the polyimide precursor comprises a repeating unit represented by the following formula (2-1). [Chemical Formula 15] In formula (2-1), R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, ^RX1 and ^RX2 each independently represent a group including a structure represented by formula (1-1) or a group represented by the following formula (R-1), and at least one of ^RX1 and ^RX2 represents a group including a structure represented by formula (1-1). [Chemical Formula 16] In the formula (R-1), ^A3 represents an oxygen atom or NH, ^RX3 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with ^R115 .

In formula (2-1), R ¹¹¹ and R ¹¹⁵ have the same meanings as R ¹¹¹ and R ¹¹⁵ in formula (2), and preferred embodiments are also the same.

In formula (2-1), at least one of ^RX1 and ^RX2 represents a group containing the structure represented by formula (1-1). The group containing the structure represented by the above formula (1-1) is preferably a group represented by the following formula (X-1). [Chemical Formula 17] In formula (X-1), ^R1 and ^R2 each independently represent an aliphatic group or an aromatic group, the carbon atom or the alkyl group of the aliphatic group or the aromatic group may be substituted by a heteroatom, ^X1 represents an oxygen atom or a sulfur atom, ^L1 represents -C(=O)- or -S(=O) _2- , and * represents a bonding site with ^R115 . In formula (X-1), ^R1 , ^R2 , ^X1 and ^L1 have the same meanings as ^R1 , ^R2 , ^X1 and ^L1 in formula (1-1), and preferred embodiments are also the same. In formula (X-1), ^R3 has the same meaning as ^R23 in formula (1-2), and preferred embodiments are also the same.

As specific examples of the group represented by formula (X-1), the following groups can be cited, but the group is not limited thereto. In the following formula, * represents a bonding site with R ^115. [Chemical Formula 18]

In formula (2-1), one of ^RX1 and ^RX2 may be a group represented by formula (R-1). In formula (R-1), ^A3 and ^RX3 have the same meanings as ^A2 and ^R113 in formula (2), respectively, and the preferred embodiments are also the same.

The content of the repeating unit represented by formula (2-1) in the polyimide precursor is not particularly limited, as long as the molar amount of the structure represented by formula (1-1) relative to the total solid content of the resin composition is appropriately adjusted to be within the above range. The content of the group represented by formula (X-1) in the polyimide precursor is preferably 0.01 to 1.0 mmol/g, and more preferably 0.01 to 0.85 mmol/g.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, for example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is still further preferred, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is a value calculated using weight average molecular weight/number average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer having an organic solvent as a main component. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more relative to 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of the polyimide, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulation of the obtained cured film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, "main chain" refers to the longest bond in the molecule of the polymer compound constituting the resin, and "side chain" refers to other bonds.

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

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

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

[Chemical formula 19]

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

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

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 20] In formula (R1) to formula (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of them, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In formula (R1) to formula (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), X is preferably an oxygen atom. In formula (R1) to formula (R3), * has the same meaning as * in formula (IV), and the preferred embodiment is also the same. The structure represented by formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (for example, 2-isocyanateethyl methacrylate). The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (e.g., glycidyl methacrylate, etc.). As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups is preferred, polyethoxy or polypropoxy is more preferred, and polyethoxy is further preferred. In the group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferred aspects of the repetition numbers of the ethoxy group and the like in these groups are as described above.

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

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

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

-Polarity Converting Group- The polyimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value- When polyimide is subjected to alkaline development, from the viewpoint of improving the developing property, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Furthermore, when the polyimide is subjected to development using a developer having an organic solvent as a main component (for example, "solvent development" described below), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, as the acid group contained in the polyimide, from the viewpoint of both storage stability and development properties, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred. pKa is a negative common logarithm pKa of the equilibrium constant Ka in consideration of the dissociation reaction of releasing hydrogen ions from an acid. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

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

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and has a polymerizable group. Formula (4) [Chemical Formula 21] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide. [Chemical Formula 22] In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4). [Chemical formula 23] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

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

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

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

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

^R132 may be a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. As a specific example, ^R115 in the formula (2) of the polyimide precursor may be cited. From the viewpoint of the strength of the cured film, ^R132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18), and as R ¹³² , more preferred examples include the above-mentioned (DAA-1) to (DAA-5).

In the case where the polyimide includes the structure represented by formula (1-1), the structure represented by formula (1-1) may be located at the end of the polyimide as shown in the following formula (2-2). [Chemical Formula 24] In formula (2-2), R ¹³¹ represents a divalent organic group, R ¹³² represents a tetravalent organic group, ^RX1 and ^RX2 each independently represent a group or an organic group containing the structure represented by formula (1-1), and at least one of ^RX1 and ^RX2 is a group containing the structure represented by formula (1-1). In formula (2-2), R ¹³¹ and R ¹³² have the same meanings as R ¹³¹ and R ¹³² in formula (4), and preferred embodiments are also the same. In formula (2-1), at least one of ^RX1 and ^RX2 represents a group containing the structure represented by formula (1-1). It is preferred that the group containing the structure represented by the above formula (1-1) is a group represented by the above formula (X-1).

In formula (2-1), one of ^RX1 and ^RX2 may be the group represented by the above formula (R-1).

Furthermore, when the polyimide includes the structure represented by formula (1-1), the polyimide may include the structure represented by formula (2-1). When the polyimide includes the structure represented by formula (2-1), at least one of ^RX1 and ^RX2 in formula (2-1) may be ring-closed to form an imide ring.

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

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

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

- Imidization rate (ring closure rate) - From the viewpoint of film strength and insulation of the obtained cured film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The upper limit of the imidization rate is not particularly limited as long as it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ^-1 , which is the absorption peak derived from the imide structure, is obtained. Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to obtain the peak intensity P2 near 1377 cm ^-1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

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

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

The weight average molecular weight (Mw) of the polyimide can be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when containing two or more polyimides, it is preferred that the weight average molecular weight of at least one polyimide is within the above range.

[Method for producing polyimide precursors, etc.] Polyimide precursors, etc. are obtained by reacting dicarboxylic acid or dicarboxylic acid derivatives with diamines. Preferably, dicarboxylic acid or dicarboxylic acid derivatives are halogenated using a halogenating agent such as sulfite chloride and then reacted with diamines.

Furthermore, it is also preferable to use a non-halogen catalyst for synthesis instead of the above-mentioned halogenating agent. As the above-mentioned non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, for example, boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, and carbodiimide compounds can be mentioned. As the above-mentioned carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, (2,6-diisopropylphenyl)carbodiimide, etc. can be mentioned.

In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds. As the organic solvent, it can be appropriately specified according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (DDM), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be produced by cyclizing the polyimide precursor by thermal imidization, chemical imidization (for example, by promoting the cyclization reaction by causing a catalyst to act), etc., after synthesizing the polyimide precursor, or directly synthesizing the polyimide.

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

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

-Introduction of the structure represented by formula (1-1)- When the specific resin contains the structure represented by formula (1-1), the specific resin is synthesized, for example, by the method described in (1) or (2) below. (1) In the method for producing the polyimide precursor, a carbodiimide compound is used as a non-halogen catalyst, and the reaction time, reaction temperature, and timing of adding the carbodiimide compound are appropriately adjusted. (2) The polyimide precursor or polyimide obtained by the method for producing the polyimide precursor and the carbodiimide compound are reacted in a solvent. As specific examples of these methods, the methods described in the synthesis examples described below can be cited, but are not limited to these.

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

<Specific compound> The resin composition of the present invention preferably includes a compound having a structure represented by the above formula (1-1) and a compound different from the above resin (specific compound).

The specific compound includes the structure represented by formula (1-1), and other than that, there is no particular limitation, but a low molecular weight compound is preferred. Specifically, the molecular weight of the specific compound is preferably 75 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.

The specific compound is preferably a compound represented by the following formula (3-1). [Chemical Formula 25] In formula (3-1), ^R1 and ^R2 each independently represent an aliphatic group or an aromatic group, the carbon atom or the hydrocarbon group of the aliphatic group or the aromatic group may be substituted by a heteroatom, ^X1 represents an oxygen atom or a sulfur atom, ^L1 represents -C(=O)- or -S(=O) _2- , ^R3 represents a hydrogen atom or a monovalent organic group, ^R4 represents a monovalent organic group, and at least two of ^R1 , ^R2 , ^R3 and ^R4 may be bonded to form a ring structure.

In formula (3-1), R ¹ , R ² , X ¹ and L ¹ have the same meanings as R ¹ , R ² , X ¹ and L ¹ in formula (1-1), respectively, and preferred embodiments thereof are also the same. In formula (3-2), R ³ has the same meaning as R ²³ in formula (1-2), and preferred embodiments thereof are also the same.

In formula (3-1), ^R4 is a monovalent organic group, preferably a alkyl group. As the above-mentioned alkyl group, an aliphatic alkyl group or an aromatic alkyl group is preferred, and an aromatic alkyl group is more preferred. As the above-mentioned aliphatic alkyl group, a saturated aliphatic alkyl group having 1 to 20 carbon atoms is preferred, and a saturated aliphatic alkyl group having 3 to 10 carbon atoms is more preferred. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 20 carbon atoms is preferred, and a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. The monovalent organic group in ^R4 may have a substituent, and examples of the substituent include an alkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like. Among them, R ⁴ is preferably a phenyl group, an alkylphenyl group or an alkoxycarbonylphenyl group, and more preferably a phenyl group, a tert-butylphenyl group or an alkoxycarbonylphenyl group in which the alkyl group has 1 to 4 carbon atoms.

In formula (3-1), at least two of R ¹ , R ² , R ³ and R ⁴ may be bonded to form a ring structure. Examples of the ring structure to be formed include a hydantoin ring, an N-acyl imidazolidinone ring, etc., but the ring structure is not limited thereto. In the present invention, an aspect in which any one of R ¹ , R ² , R ³ and R ⁴ does not form a ring structure is also one of the preferred aspects.

Specific examples of preferred embodiments of the specific compound are given below, but the present invention is not limited thereto. [Chemical Formula 26] [Chemical formula 27]

When the resin composition contains a specific compound, its content is not particularly limited, as long as the molar amount of the structure represented by formula (1-1) relative to the total solid content of the resin composition is appropriately adjusted to an amount within the above range. In addition, when the resin composition contains a specific compound, its content is preferably 0.01 to 1.0 mass % relative to the total solid content of the resin composition of the present invention, 0.01 to 0.85 mass % is more preferably, and 0.015 to 0.75 mass % is further preferably. The specific compound can be used alone, but two or more can also be used. When two or more are used simultaneously, it is preferred that the total amount be within the above range.

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

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

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

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

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

As the sulfoxides, dimethyl sulfoxide can be preferably mentioned, for example.

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

As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

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

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

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

From the viewpoint of coating properties, the content of the solvent is preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 5 to 80 mass %, more preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 5 to 75 mass %, further preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 10 to 70 mass %, and further preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 40 to 70 mass %. The content of the solvent can be adjusted according to the desired thickness of the coating film and the coating method.

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

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

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more relative to the total solid content of the composition. In addition, the content of the other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less relative to the total solid content of the composition. In addition, as a preferred embodiment of the composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount be within the above range.

<Polymerization initiator> The resin composition of the present invention preferably contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred.

[Photopolymerization initiator] The 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, it can also be an activator that generates active radicals by reacting with a photoexcited sensitizer in some way.

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

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketone oxime 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.

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

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

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

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application 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) can be used.

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

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

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

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

[Chemical formula 28]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 29]

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

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

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

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

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

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

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

[Chemical formula 30]

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

[Chemical formula 31]

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

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

When a photopolymerization initiator is included, its content 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 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 contained, the total amount thereof is preferably within the above range.

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

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

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

[Photoacid generator] In addition, the composition of the present invention may contain a photoacid generator. By containing a photoacid generator, for example, acid is generated in the exposed part of the composition layer, and the solubility of the exposed part in the developer (for example, alkaline aqueous solution) is increased, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, it is also possible to set it as follows: by containing a photoacid generator and a polymerizable compound other than a free radical polymerizable compound described later, for example, the acid generated in the exposed part is used to promote the crosslinking reaction of the polymerizable compound, so that the exposed part is less likely to be removed by the developer than the non-exposed part. According to such an aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimidesulfonates, oximesulfonates, diazodisulfonates, disulfonates, and o-nitrobenzylsulfonates.

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

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

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

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

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

[Chemical formula 32]

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

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

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

[Chemical formula 33]

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

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

In formula (OS-103) to formula (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by ^Rs6 may have a substituent. In formula (OS-103) to formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 34]

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

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

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

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

[Chemical formula 35]

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

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

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In addition, in the above oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or a mixture. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 36] In addition, commercial products may be used as the photoacid generator. Examples of commercial products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

As a more preferred example, the compound represented by the following structural formula can also be cited. [Chemical Formula 37]

As photoacid generators, organic halogenated compounds can also be used. As organic halogenated compounds, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, can be cited as trihalomethyl-substituted azole compounds: S-trioxane compounds. More preferably, s-trioxane derivatives formed by at least one mono-, di- or trihalomethyl-substituted methyl group bonded to the s-trioxane ring can be cited. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-trioxane, 2,4,6-tris(dichloromethyl)-s-trioxane, 2,4,6-tris(trichloromethyl)-s-trioxane, 2-methyl-4,6-bis(trichloromethyl)-s-trioxane, 2-n-propyl-4,6-bis(trichloromethyl)-s-trioxane can be cited. -trisinium, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-phenyl-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-〔1-(p-methoxyphenyl)- phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(4-naphthyloxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, s-triazine, 2-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc.

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

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

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

As the onium salt, there can be mentioned onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 38] In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. _Z21- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a ^thiosulfonic acid ion, or a sulfate ion. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, or carboxylic acid ions are preferred. In formula (RI-III), _R31 , _R32 , and _R33 each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms and which may have 1 to 6 substituents. In terms of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

As a specific example, the following can be cited. [Chemical formula 39] [Chemical formula 40] [Chemical formula 41] [Chemical formula 42]

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

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

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

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the cured film and less deterioration of the physical properties of the cured film, those that produce alkylsulfonic acids having 1 to 4 carbon atoms or halogenated alkylsulfonic acids having 1 to 4 carbon atoms are more preferred, such as (4-hydroxyphenyl)dimethylcoppersulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcoppersulfonate, benzyl(4-hydroxyphenyl)methylcoppersulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coppersulfonate, (4-hydroxyphenyl)dimethylcoppersulfonate, Preferred as the thermal acid generator are (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

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

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

<Onium salt> The resin composition of the present invention may further contain an onium salt. In particular, when the resin composition of the present invention contains a polyimide precursor as a specific resin, it is preferable to contain an onium salt. The type of onium salt is not particularly specified, and preferably ammonium salts, ammonium salts, cobalt salts, iodine salts, or phosphonium salts can be cited. Among them, ammonium salts or ammonium salts are preferable from the viewpoint of high thermal stability, and cobalt salts, iodine salts, or phosphonium salts are preferable 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 cation part and anion part in the same molecular structure, or an intermolecular salt formed by ionic bonding between cation molecules and anion molecules of different molecules, but intermolecular salts are preferred. Furthermore, in the resin composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ionic bonding or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a coronium cation, an iodine cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

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

When the 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 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, 10 mass % or less is further preferred, and it can also be 5 mass % or less, and it can also be 4 mass % or less. The onium salt can be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

<Thermal alkali generator> The resin composition of the present invention may further contain a thermal alkali generator. In particular, when the resin composition of the present invention contains a polyimide precursor as a specific resin, it is preferable to contain a thermal alkali generator. Other thermal alkali generators may be compounds corresponding to the above-mentioned onium salts, or thermal alkali generators other than the above-mentioned onium salts. As thermal alkali generators other than the above-mentioned onium salts, non-ionic thermal alkali generators can be cited. As non-ionic thermal alkali generators, compounds represented by formula (B1) or formula (B2) can be cited. [Chemical Formula 43]

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

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

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

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

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 44]

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

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

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

The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 45]

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

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

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

[Chemical formula 46]

[Chemical formula 47]

[Chemical formula 48]

The content of other alkali generators is preferably 0.1 to 50% by mass relative to the total solid content of the 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

As the free radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, or urethane compounds having an ethylene oxide structure described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

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

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

From the viewpoint of pattern resolution and film stretchability, the resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hex ... Dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and bifunctional acrylate with carbamate bond, bifunctional methacrylate with carbamate bond. Two or more of these can be used in combination as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Furthermore, from the viewpoint of suppressing the warping caused by the control of the elastic modulus of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

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

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

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

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

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoprop ... Glycoluril-based crosslinking agents such as methylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea; Monohydroxymethylated ethylurea or dihydroxymethyl Ethyl urea crosslinking agents such as ethyl urea, monomethoxymethyl ethyl urea, dimethoxymethyl ethyl urea, monoethoxymethyl ethyl urea, diethoxymethyl ethyl urea, monopropoxymethyl ethyl urea, dipropoxymethyl ethyl urea, monobutoxymethyl ethyl urea or dibutoxymethyl ethyl urea; Monohydroxymethyl ethyl urea, dihydroxymethyl ethyl urea, monomethoxymethyl ethyl urea, dimethoxymethyl ethyl urea, monoethoxymethyl ethyl urea, diethoxymethyl ethyl urea, monopropoxymethyl ethyl urea, dipropoxymethyl ethyl urea, monobutoxymethyl ethyl urea or dibutoxymethyl ethyl urea; Propylene urea crosslinking agents such as methylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

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

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

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

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

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

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy epoxy silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICL ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

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

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

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

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

<Migration inhibitor> The 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 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, triazole ring, imidazole ring, isobutylene ring, thiazole ring, pyrazole ring, isobutylene ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, tributylene ring), compounds having thiourea and thiohydrin, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the 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 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 resin composition, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %.

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

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

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) can be preferably used. , N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiophene, N-nitrosodiphenylamine, N-phenylnaphthylamine, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine First arsenic salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1 -oxyl radical, phenothiocyanate, 1,1-diphenyl-2-picrylhydrazine, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, 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 resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0 mass %, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % relative to the total solid content of the resin composition of the present invention.

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

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

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

[Chemical formula 51] As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-butylenepropyl methyldimethoxysilane, 3-butylenepropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

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

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

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting it to be above the lower limit, the adhesion between the cured film and the metal layer after the curing step becomes good, and by setting it to be below the upper limit, the heat resistance and mechanical properties of the cured film after the curing step 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 amount is within the above range.

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

[Sensitizer] The resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermosetting accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermosetting accelerator, the thermal free radical polymerization initiator, and the photo-free radical polymerization initiator cause chemical changes and decompose, thereby generating free radicals, acids or bases. Examples of the sensitizer include michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-Dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-pyrrolidone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Amyl ester, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As the sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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

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

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

When the 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 resin composition of the present invention. The chain transfer agent may be only one kind or may be two or more kinds. When there are two or more kinds of chain transfer agents, it is preferred that the total amount of the chain transfer agents is within the above range.

[Surfactant] From the viewpoint of further improving the coating properties, various types of surfactants can be added to the 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] In addition, the surfactant may also use the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219. As for the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain may also be used as the fluorine-based surfactant. As specific examples, there may be cited the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation.

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

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

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

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

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

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

When the 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 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, the resin composition of the present invention may add a higher fatty acid derivative such as behenic acid or behenic acid amide so that it is unevenly distributed on the surface of the resin composition during the drying process after coating.

Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the 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 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 content thereof is preferably within the above range.

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

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

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

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

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

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

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

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

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

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

[Chemical formula 53]

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

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

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

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

[Chemical formula 54]

[Chemical formula 55]

[Chemical formula 56]

[Chemical formula 57]

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

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

From the perspective of insulation, the metal content of the 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.

In addition, as a method for reducing the metal impurities accidentally contained in the 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 resin composition of the present invention; filtering the raw material constituting the resin composition of the present invention with a filter; lining the device with polytetrafluoroethylene or the like and distilling under conditions that suppress contamination as much as possible.

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

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

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

<Preparation of resin composition> The 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 using a conventionally known method.

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

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

The cured film of the present invention is a cured film formed by curing the resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, or 1 μm or more, and the upper limit can be set to 100 μm or less, or 30 μm or less.

The cured film of the present invention can be stacked in 2 or more layers, and further stacked in 3 to 7 layers to form a laminate. The laminate of the present invention is preferably a laminate including 2 or more cured films and a metal layer between any of the above-mentioned cured films. For example, a laminate having a layered structure including at least three layers stacked in sequence, namely, a first cured film, a metal layer, and a second cured film, can be cited as a preferred example. The above-mentioned first cured film and the above-mentioned second cured film are both the cured films of the present invention. As a preferred example, for example, any one of the above-mentioned first cured film and the above-mentioned second cured film can be cited as a film formed by curing the resin composition of the present invention. The resin composition of the present invention used for forming the first cured film and the resin composition of the present invention used for forming the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a redistribution layer.

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

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

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

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

<Membrane forming step (layer forming step)> The manufacturing method of the preferred embodiment of the present invention includes a membrane forming step (layer forming step) of applying a resin composition to a substrate to form a membrane (layer).

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

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

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

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

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

<Exposure step> The manufacturing method of the present invention may include an exposure step of exposing the above-mentioned film (resin composition layer). There is no particular regulation on the exposure amount as long as the resin composition can be cured. 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, preferably 240 to 550 nm.

If we explain the exposure wavelength in relation to the light source, we can cite (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 (three 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 light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of the YAG laser is 532nm and the third harmonic is 355nm. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, high exposure sensitivity can be obtained. In addition, from the perspective of operation and productivity, a wide (three wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred.

<Developing step> The manufacturing method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (resin component layer). The unexposed portion (non-exposed portion) is removed by developing. There is no particular limitation on the developing method as long as the desired pattern can be formed. For example, spraying developer from a nozzle, spraying mist, immersing the substrate in developer, etc. can be cited. Spraying from a nozzle can be preferably used. The developing step may include a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially stationary state, a step of vibrating the developer using ultrasound or the like, and a step of combining these.

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

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

In the case where the developer contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate), , ethyl ethoxylate, etc.)), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl ester)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea acetate, diethylene glycol monomethyl ether, Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably exemplified, and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably exemplified, as sulfoxides, for example, dimethyl sulfoxide is preferably exemplified, and mixtures of these organic solvents are also preferably exemplified.

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

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

[Developer supply method] There are no particular restrictions on the developer supply method as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate by immersion development, or continuously supplying the developer. There are no particular restrictions on the type of nozzle, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, the method of supplying the developer with a vertical nozzle or the method of continuously supplying with a spray nozzle is preferred. From the perspective of developer permeability to the image area, the method of supplying with a spray nozzle is more preferred. Also, after continuously supplying the developer with a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a vertical nozzle again, and the substrate is rotated to remove the developer from the substrate, and this step can be repeated multiple times. Also, as a method for supplying the developer in the developing step, there can be a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate using ultrasound or the like, and a step of combining these steps.

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

[Developer supply method] There are no particular restrictions on the developer supply method as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate by immersion development, or continuously supplying the developer. There are no particular restrictions on the type of nozzle, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, the method of supplying the developer with a vertical nozzle or the method of continuously supplying with a spray nozzle is preferred. From the perspective of developer permeability to the image area, the method of supplying with a spray nozzle is more preferred. Also, after continuously supplying the developer with a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a vertical nozzle again, and the substrate is rotated to remove the developer from the substrate, and this step can be repeated multiple times. Also, as a method for supplying the developer in the developing step, there can be a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate using ultrasound or the like, and a step of combining these steps.

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

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

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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.)), alkyl 3-alkoxy propionates (e.g., 3-alkoxy methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, etc.), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, etc.), methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate Ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and, as ethers, for example, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably exemplified, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably exemplified, as sulfoxides, for example, dimethyl sulfoxide is preferably exemplified, and as alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, triethylene glycol, etc. are preferably exemplified, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably exemplified.

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

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

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

[Method for supplying rinse liquid] There are no particular restrictions on the method for supplying rinse liquid as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, performing rotary immersion development on the substrate, supplying the rinse liquid to the substrate with a sprayer, and continuously supplying the developer to the substrate using a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. There is no particular limitation on the type of nozzle, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure using a vertical nozzle, and it is more preferably a step of supplying the rinsing liquid using a spray nozzle. In addition, as a method of supplying the developer in the rinsing step, it is possible to adopt a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid on the substrate in a substantially stationary state, a step of vibrating the rinsing liquid on the substrate using ultrasound, etc., and a step of combining these methods.

<Heating step> The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450°C (heating step). It is preferred to include a heating step after the film forming step (layer forming step), the drying step and the developing step. In the heating step, for example, a cyclization reaction of the specific resin precursor is carried out by generating a base by decomposing the above-mentioned hot alkali generator. In addition, the resin composition of the present invention may contain a free radical polymerizing compound other than the specific resin precursor, but it is also possible to perform curing of free radical polymerizing compounds other than the unreacted specific resin precursor in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, further preferably 160°C or higher, and further preferably 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, further preferably 350°C or lower, further preferably 250°C or lower, and further preferably 220°C or lower.

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 volatility of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when a 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 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, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is not clear, but it is believed that the reason is that the acetylene groups of the specific resin between the layers undergo cross-linking reaction by setting the temperature to this level.

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

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

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

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

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

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

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

<Lamination step> The manufacturing method of the present invention preferably also includes a layering step.

The lamination step includes a series of steps including (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step, which are sequentially performed again on the surface of the hardened film (resin layer) or metal layer. However, it is also possible to perform only (a) film formation step repeatedly. In addition, it is also possible to perform (d) heating step at the end or in the middle of the lamination. That is, it is possible to perform (a) to (c) repeatedly for a specified number of times, and then perform (d) heating, so that the deposited resin composition layer is cured collectively. Furthermore, after the (c) developing step, the (e) metal layer forming step may be included. In this case, the heating in (d) may be performed each time, or may be performed all at once after a specified number of layering steps. It is self-evident that the above-mentioned drying step or heating step may be appropriately included in the layering step.

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

The above-mentioned lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. In addition, each layer in the lamination step may be a layer of the same composition, shape, film thickness, etc., or may be a different layer.

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, in which the number of resin layers is 2 or more and 20 or less is preferred, a structure of resin layer of 3 or more and 7 or less is more 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 resin composition so as to cover the metal layer. Specifically, there can be cited an embodiment in which (a) film forming step, (b) exposure step, (c) development step, (e) metal layer forming step, and (d) heating step are repeated in this order, or an embodiment in which (a) film forming step, (b) exposure step, (c) development step, and (e) metal layer forming step are repeated in this order and (d) heating step is provided at the end or in the middle. By alternately performing the step of laminating the resin composition layer (resin layer) and the step of forming the metal layer, the 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 resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Publication No. 2016-027357, which are incorporated into this specification.

(Surface activation treatment step) The method for manufacturing a laminate of the present invention may include a surface activation treatment step of performing surface activation treatment on at least a portion of the above-mentioned metal layer and the photosensitive resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the above-mentioned exposure and development step and then after the photosensitive resin composition layer is subjected to the surface activation treatment step. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed photosensitive resin composition layer, or may be performed separately on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or resin layer disposed on the surface subjected to surface activation treatment can be improved. Specifically, the surface activation treatment includes plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of immersing in an organic surface treatment agent containing at least one compound of an amino group and a thiol group after removing the oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ^2. [Example]

The following examples are given to further illustrate the present invention. 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 polyimide precursor (A-1) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 14.06 g (64.5 mmol) of pyromellitic acid dianhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) 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 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. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0°C over 20 minutes. Next, the reaction mixture was reacted at 0°C for 1 hour, and then 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 (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, and was 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 to obtain polyimide precursor A-1. The weight average molecular weight of the polyimide precursor A-1 was 19,000. The obtained polyimide precursor A-1 is estimated to contain repeating units represented by the following formula (A-1). [Chemical Formula 58]

<Synthesis Example 2> [Synthesis of polyimide precursor (A-2) from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (obtained by drying 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 (water content 88 ppm) were mixed and stirred at 60°C for 18 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and polyimide precursor A-2 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor A-2 was 20,000. It is inferred that the obtained polyimide precursor A-2 contains repeating units represented by the following formula (A-2). In the repeating unit represented by the formula (A-2), a single bond contained in the biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride and an ester structure formed from 3,3',4,4'-biphenyltetracarboxylic anhydride and 2-hydroxyethyl methacrylate may exist at the meta position or at the para position on the benzene ring (for example, the repeating unit represented by the following formula (A-2-2)). It is considered that these structures exist in a mixed state in the polyimide precursor A-2. Similarly, in the chemical formula representing the repeating units contained in the polyimide precursor produced when 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxyphthalic anhydride is used as the acid dianhydride in the following synthesis example, the positional relationship on the benzene ring of the single bond contained in the biphenyl structure of 3,3',4,4'-biphenyltetracarboxylic anhydride or the ether bond contained in 4,4'-oxyphthalic anhydride and the ester bond and amide bond bonded to the benzene ring contained in each repeating unit is not limited to the structure described as the chemical formula, and those having different positional relationships as described above may also exist in a mixed manner. [Chemical Formula 59]

<Synthesis Example 3> [Synthesis of polyimide precursor (A-3) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) 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 acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and polyimide precursor A-3 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor A-3 was 18,000. It is estimated that the obtained polyimide precursor A-3 contains repeating units represented by the following formula (A-3). [Chemical Formula 60]

<Synthesis Example 4> [Synthesis of polyimide precursor (A-4) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diethylene glycol dimethyl ether (water content 67 ppm) were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid 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 polyimide precursor A-4 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor A-4 was 19,000. It is estimated that the obtained polyimide precursor A-4 contains repeating units represented by the following formula (A-4). [Chemical Formula 61]

<Synthesis Example 5> [Synthesis of polyimide precursor (A”-5) from 4,4’-oxydiphthalic anhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] Mix 20.0 g (64.5 mmol) of 4,4’-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 200g of γ-butyrolactone was stirred at room temperature for 36 hours to produce the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, under ice cooling, a solution of 26.6g of dicyclohexylcarbodiimide (DCC) dissolved in 25g of γ-butyrolactone was added dropwise while stirring. Then, 12.0g of 4,4'-diaminodiphenyl ether suspended in 45ml of γ-butyrolactone and DCCC were added simultaneously over 60 minutes while stirring. 3.8 g of ethanol was dissolved in 10 g of γ-butyrolactone. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 100 ml of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution. Then, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimide precursor mixture was spun at 5,000 rpm (revolutions per The mixture was stirred at a speed of 200 rpm for 15 minutes. The polyimide precursor was obtained by filtration, dissolved in 300 mL of tetrahydrofuran, and then obtained again as a precipitate in 2 liters of water. The obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain polyimide precursor A”-5. The weight average molecular weight of the polyimide precursor A”-5 was 22,000.

<Synthesis Example 6> [Synthesis of polyimide precursor (A”-6) from pyromellitic dianhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 14.1 g (64.5 mmol) of pyromellitic dianhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 2 00 g of γ-butyrolactone was stirred at room temperature for 36 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, the diester was converted into a polyimide precursor using 4,4'-diaminodiphenyl ether using DCC in the same manner as in Synthesis Example 5, and a polyimide precursor A"-6 was obtained in the same manner as in Synthesis Example 5. The weight average molecular weight of the polyimide precursor A"-6 was 20,000.

<Synthesis Example 7> [Synthesis of polyimide precursor (A”-7) from 3,3’,4,4’-biphenyltetracarboxylic anhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 19.0 g (64.5 mmol) of 3,3’,4,4’-biphenyltetracarboxylic anhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20.4 g (258 mmol) of pyridine and 200 g of γ-butyrolactone were stirred at room temperature for 36 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, the obtained diester was converted into a polyimide precursor using 4,4'-diaminodiphenyl ether using DCC in the same manner as in Synthesis Example 5, and a polyimide precursor A"-7 was obtained in the same manner as in Synthesis Example 5. The weight average molecular weight of the polyimide precursor A"-7 was 21,000.

<Synthesis Example 8> [Synthesis of polyimide precursor (A”-8) from 4,4’-oxydiphthalic anhydride, 4,4’-diamino-2,2’-dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate] 19.0 g (64.5 mmol) of 4,4’-oxydiphthalic anhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of ) of pyridine and 200 g of γ-butyrolactone were stirred at room temperature for 36 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, using DCC, the obtained diester was converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) in the same manner as in Synthesis Example 5, and a polyimide precursor A"-8 was obtained in the same manner as in Synthesis Example 5. The weight average molecular weight of the polyimide precursor A"-8 was 19,000.

<Synthesis Example 1-1> [Modification of polyimide precursor A-1 from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (Synthesis of polyimide precursor A'-1)] 20 g of the polyimide precursor A-1 obtained in Synthesis Example 1 was dissolved in 200 g of tetrahydrofuran. Then, under ice-cooling, a solution of 13.0 g of DCC dissolved in 50 g of tetrahydrofuran was added dropwise while stirring. Stirring was continued for 2 hours under ice-cooling. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution. Next, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, and the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain polyimide precursor A'-1. The weight average molecular weight of the polyimide precursor A'-1 is 20,500. It is estimated that the polyimide precursor A'-1 contains repeating units of the structure represented by the following formula (A'-1). [Chemical Formula 62]

<Synthesis Example 2-1> [Modification of polyimide precursor A-2 from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (Synthesis of polyimide precursor A'-2)] In Synthesis Example 1-1, polyimide precursor A'-2 as a modified polyimide precursor was obtained in the same manner as in Synthesis Example 1-1, except that 20 g of polyimide precursor A-2 obtained in Synthesis Example 2 was used instead of polyimide precursor A-1. The weight average molecular weight of the polyimide precursor A'-2 was 21,200. It is speculated that the polyimide precursor A'-2 contains repeating units of the structure represented by the following formula (A'-2). [Chemical Formula 63]

<Synthesis Example 3-1> [Modification of polyimide precursor A-3 from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (Synthesis of polyimide precursor A'-3)] In Synthesis Example 1-1, polyimide precursor A'-3 as a modified polyimide precursor was obtained in the same manner as in Synthesis Example 1-1, except that 20 g of polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of polyimide precursor A-1. The weight average molecular weight of the polyimide precursor A'-3 was 18,500. It is speculated that the polyimide precursor A'-3 contains repeating units of the structure represented by the following formula (A'-3). [Chemical Formula 64]

<Synthesis Example 4-1> [Modification of polyimide precursor A-4 from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-4)] In Synthesis Example 1-1, except that 20 g of polyimide precursor A-4 obtained in Synthesis Example 4 was used instead of polyimide precursor A-1, a modified polyimide precursor A'-4 was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-4 was 20,500. It is estimated that the polyimide precursor A'-4 contains repeating units of the structure represented by the following formula (A'-4). [Chemical Formula 65]

<Synthesis Example 5-1> [Modification of polyimide precursor A-2 from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-5)] In Synthesis Example 1-1, 20 g of polyimide precursor A-2 obtained in Synthesis Example 2 was used instead of polyimide precursor A-1, and diisopropylcarbodiimide (DIC) was used instead of DCC. Modified polyimide precursor A'-5 was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-5 was 21,000. It is estimated that the polyimide precursor A'-5 contains repeating units of the structure represented by the following formula (A'-5). [Chemical Formula 66]

<Synthesis Example 6-1> [Modification of polyimide precursor A-2 from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-6)] In Synthesis Example 1-1, except that 20 g of polyimide precursor A-2 obtained in Synthesis Example 2 was used instead of polyimide precursor A-1, and (2,6-diisopropylphenyl)carbodiimide (DIPC) was used instead of DCC, a modified polyimide precursor A'-6 was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-6 was 21,500. It is estimated that the polyimide precursor A'-6 contains repeating units of the structure represented by the following formula (A'-6). [Chemical Formula 67]

<Synthesis Example 7-1> [Modification of polyimide precursor A-3 from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-7)] In Synthesis Example 1-1, except that 20 g of polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of polyimide precursor A-1, and DIC was used instead of DCC, a modified polyimide precursor A'-7 was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-7 was 19,000. It is estimated that the polyimide precursor A'-7 contains repeating units of the structure represented by the following formula (A'-7). [Chemical Formula 68]

<Synthesis Example 8-1> [Synthesis of polyimide P-1] In a flask equipped with a condenser and a stirrer, 11.4 g (25 mmol) of anhydride (a-1) represented by the following formula (a-1) was dissolved in 33.1 g of N-methylpyrrolidone (NMP) while removing water. Then, 2.70 g (25 mmol) of 1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1.2 liters of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain closed-ring polyimide P-1. The molecular weight of P-1 is weight average molecular weight (Mw) = 74,300, number average molecular weight (Mn) = 30,100. The structure of P-1 is estimated to be the structure represented by the following formula (P-1). [Chemical formula 69]

<Synthesis Example H-1> 41.3 g (0.20 mol) of dicyclohexylcarbodiimide and 200 mL of tetrahydrofuran were mixed in a three-necked flask. Then, a solution of 24.4 g (0.02 mol) of benzoic acid dissolved in 200 mL of tetrahydrofuran was added dropwise to the flask at room temperature over 30 minutes using a dropping funnel. After the addition was completed, the reaction was continued at room temperature for 30 minutes and then allowed to stand for 24 hours. The precipitate was filtered and the filtrate was recovered. After the recovered filtrate (THF solution) was concentrated, compound H-1 was obtained as a white powder by recrystallization. The structure of compound H-1 is estimated to be the structure represented by the formula (H-1) described below.

<Synthesis Example H-2> Compound H-2 was obtained by the same method as in Synthesis Example H-1 except that 36.0 g (0.2 mol) of monomethyl phthalate was used instead of benzoic acid. The structure of Compound H-2 is estimated to be the structure represented by the formula (H-2) described below.

<Synthesis Example H-3> In Synthesis Example H-1, except that dicyclohexylcarbodiimide was replaced with 44.5 g (0.2 mol) of 1,3-di-p-tricarbodiimide and benzoic acid was replaced with 35.2 g (0.2 mol) of 4-tert-butylbenzoic acid, the same method as Synthesis Example H-1 was used to obtain Compound H-3. The structure of Compound H-3 is estimated to be the structure represented by the formula (H-3) described below.

<Synthesis Example H-4> In Synthesis Example H-1, except that dicyclohexylcarbodiimide was replaced with 44.5 g (0.2 mol) of 1,3-di-p-tricarbodiimide and benzoic acid was replaced with 36.0 g (0.2 mol) of monomethyl phthalate, the same method as Synthesis Example H-1 was used to obtain Compound H-4. The structure of Compound H-4 is estimated to be the structure represented by the formula (H-4) described below.

<Synthesis Example H-5> In Synthesis Example H-1, except that dicyclohexylcarbodiimide was replaced with 72.5 g (0.2 mol) of bis(2,6-diisopropylphenyl)carbodiimide, a compound H-5 was obtained in the same manner as in Synthesis Example H-1. The structure of the compound H-5 is estimated to be the structure represented by the formula (H-5) described below.

<Synthesis Example H-6> Compound H-6 was obtained by the same method as Synthesis Example H-1 except that dicyclohexylcarbodiimide used in Synthesis Example H-1 was replaced with 44.5 g (0.2 mol) of 1,3-di-p-tricarbodiimide and 44.4 g (0.2 mol) of monobutyl phthalate was replaced with benzoic acid. The structure of Compound H-6 is estimated to be the structure represented by the formula (H-6) described below.

<Synthesis Example H-7> 10.0 g (78 mmol) of 5,5-dimethylhydantoin and 40 mL of pyridine were mixed in a three-necked flask. 11.0 g (78 mmol) of benzyl chloride was added dropwise to the flask at room temperature over 30 minutes. After the addition was completed, the mixture was reacted at 170°C for 15 hours. After the reaction was completed, the mixture was concentrated under reduced pressure and then diluted with ethyl acetate. After filtering with silica gel, the mixture was recrystallized with ethyl acetate/hexane (a solvent prepared by mixing ethyl acetate and hexane at a volume ratio of ethyl acetate:hexane = 1:9) to obtain compound H-7 as a white powder. The structure of compound H-7 is estimated to be the structure represented by the formula (H-7) described below.

<Synthesis Example H-8> 1.26 g (10 mmol) of diisopropylcarbodiimide, 100 mL of tetrahydrofuran, and 1.41 g (10 mmol) of benzyl chloride were mixed in a three-necked flask. Stirring was continued at room temperature for 48 hours. Then, 1.04 g (10 mmol) of 1,3-dimethylthiourea was added, and stirring was continued for 12 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate/hexane (a solvent prepared by mixing ethyl acetate and hexane at a volume ratio of ethyl acetate:hexane = 1:9) to obtain compound H-8 as a white solid. The structure of compound H-8 is estimated to be represented by the following formula (H-8). [Chemical formula 70]

<Examples and Comparative Examples> In each of the Examples and Comparative Examples, the components listed in Table 1 below were mixed to obtain a resin composition or a comparative composition. The numerical values in the columns of each component other than the solvent listed in Table 1 represent the content (parts by mass) of each component. The obtained resin composition and comparative composition were pressure filtered through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Table 1, "-" indicates that the corresponding component is not contained.

[Table 1] Resin Thermoalkali generator Free Radical Polymerization Initiator Free radical polymerizable compounds Polymerization inhibitor Migration inhibitors Silane coupling agent Specific compounds Solvent Other additives Content of specific structures Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality mmol/g Embodiment 1 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 2 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 3 A'-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.09 4 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 5 A-1 34.8 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 0.2 I-1 42.2 I-2 14.1 - - J-2 1 0.014 6 A-1 33.0 B-1 0.75 C-1 1.26 D-1 4.85 E-1 0.084 F-1 0.126 G-1 0.63 H-1 10.3 I-1 36.7 I-2 12.3 - - J-2 1 0.62 7 A-3 25.2 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.01 A"-5 8.4 8 A-2 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-3 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 9 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 10 A-4 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 11 A"-6 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 12 A"-7 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 13 A"-8 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 14 A'-2 33.6 B-1 0.75 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.07 15 A'-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 16 A'-4 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 17 A-2 16.8 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 I-1 43.3 I-2 14.4 - - J-2 1 0.05 A"-7 16.8 18 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 H-2 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.09 19 A-1 33.6 B-1 0.75 C-2 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 H-3 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.09 20 A-2 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-4 1.5 I-3 56.3 - - - - J-2 1 0.09 twenty one A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 H-5 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.08 twenty two A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-6 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.08 twenty three A-3 33.6 B-1 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-7 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.15 twenty four A-2 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-8 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.12 25 A'-5 33.6 B-5 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 26 A'-6 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 27 A'-7 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 28 A-1 33.6 - - C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 2.3 I-1 42.2 I-2 14.1 - - J-2 1 0.16 29 P-1 33.6 - - C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-3 57.0 - - - - J-2 1 0.10 30 A-4 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-4 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 31 A-4 28 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 twenty two I-1 33.2 I-2 8.1 - - J-2 1 1.14 32 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - - - 0.10 33 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - - - 0.10 Comparison Example 1 A-4 35.0 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 - - I-3 56.3 - - - - J-2 1 0.00 2 A-4 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 - - I-3 56.3 - - J-1 1.5 J-2 1 0.00

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

[Resin] ・A-1 to A-4, A”-5 to A”-8, A’-1 to A’-7, P-1: polyimide precursors A-1 to A-4, polyimide precursors A”-5 to A”-8, polyimide precursors A’-1 to A’-7, polyimide P-1 synthesized in the above synthesis example

[Thermoalkali generator] ・B-1 to B-5: Compounds represented by the following formulas (B-1) to (B-5) [Chemical formula 71]

[Free radical polymerization initiator] ・C-1: IRGACURE OXE 01 (manufactured by BASF) ・C-2: IRGACURE OXE 02 (manufactured by BASF) ・C-3: IRGACURE 369 (manufactured by BASF)

[Free radical polymerizable compound] ・D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・D-2: SR-209 (manufactured by Sartomer Company, Inc., compound with the following structure) ・D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) [Chemical formula 72]

[Polymerization inhibitor] ・E-1: 2-Nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-2: p-Benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Migration inhibitor] ・F-1 to F-4: Compounds with the following structure [Chemical formula 73]

[Silane coupling agent (metal adhesion improver)] ・G-1 to G-4: compounds having the following structures. In the following structural formula, Et represents an ethyl group. [Chemical formula 74]

[Specified compounds] ・H-1 to H-8: Compounds H-1 to H-8 listed above

[Other additives] ・J-1: Compound represented by the following formula (J-1) ・J-2: N-phenyldiethanolamine [chemical formula 75]

[Solvent] ・I-1: N-methyl-2-pyrrolidone ・I-2: Ethyl lactate ・I-3: γ-butyrolactone: dimethyl sulfoxide = 80 mass %: 20 mass % mixed solvent

<Evaluation> [Quantification of specific structure] The method for quantifying the content of the specific structure when added as an additive (compounds H-1 to H-8) and when bound to a polymer is as follows.

-When added as an additive- The prepared composition is analyzed by NMR using _d6- DMSO (dimethyl sulfoxide- _d6 ), and the molar ratio of the polymer and the additive is calculated. Then, after diluting the composition with tetrahydrofuran, a mixed solvent of water:acetone = 50 mass%:50 mass% is added, the precipitate is filtered and the obtained filtrate is dried. The mass of the polymer is obtained by calculating the dry mass. The content of the additive is quantified based on the molar ratio of polymer/additive and the mass of the polymer. -When bonded to a polymer- After diluting the composition with tetrahydrofuran, a mixed solvent of water:acetone = 50 mass%:50 mass% is added, the precipitate is filtered and the obtained filtrate is dried. The mass of the polymer is obtained by calculating the dry mass. The obtained polymer is subjected to NMR analysis using d ₆ -DMSO to calculate the molar ratio of the polymer and the additive. The content of the specific structure is quantified based on the polymer mass and the molar ratio. In addition, regarding the total solid content of the resin composition, the solvent is dried under the conditions of 70°C/0.1 Torr/3 hours, and the mass of the dried residue is set as the total solid content. 1 Torr is a value representing 1/760 of 1 atmosphere, and is set to 133.322 Pa. In the above drying, the volatile component ¹ H-NMR (using DMSO (dimethyl sulfoxide)-d ₆ as a solvent) confirmed that there were no volatile components other than the solvent. The content (mol/g) of the structure represented by formula (1-1) relative to the total solid content of the resin composition was quantified by the above method, and the quantitative results were recorded in the "Content of specific structure" column of Table 1.

[Evaluation of storage stability] The viscosity of the resin composition and the comparative composition prepared in each embodiment and comparative example was measured using an E-type viscometer immediately after preparation. At this time, the measured viscosity value was set as "Viscosity (0 day)". Thereafter, the resin composition and the comparative composition in each embodiment and comparative example were placed in a sealed container under light-shielding conditions at 25°C for 14 days, and the viscosity was measured again using an E-type viscometer. At this time, the measured viscosity value was set as "Viscosity (14 days)". The viscosity change rate was calculated according to the following formula. Based on the above viscosity change rate and the following evaluation criteria, the evaluation was performed. The evaluation results are recorded in the "Storage Stability" column of Table 2. It can be said that the lower the viscosity change rate, the higher the storage stability. Viscosity change rate = |100×{1-(viscosity (14 days)/viscosity (0 days))}| The viscosity was measured at 25°C, and other measurement conditions were in accordance with JIS Z 8803:2011. -Evaluation criteria- A: The viscosity change rate is less than 5%. B: The viscosity change rate exceeds 5%.

[Evaluation of Adhesion] The resin composition or comparative composition prepared in each embodiment and comparative example was applied in a layer on a copper substrate by spin coating to form a resin composition layer or a comparative composition layer. The copper substrate on which the resin composition layer or the comparative composition layer was formed was dried on a heating plate at 100°C for 5 minutes to form a resin composition layer or a comparative composition layer having a uniform thickness of 20 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C), a photomask with a square non-mask portion of 100 μm square was used to expose the resin composition layer or the comparative composition layer on the copper substrate with i-rays at an exposure energy of 500 mJ/ ^cm2 , and then developed with cyclopentanone for 60 seconds to obtain a 100 μm square resin layer. Furthermore, the resin layer (pattern) was formed by heating at 230°C for 3 hours in a nitrogen atmosphere. In an environment of 25°C and 65% relative humidity (RH), the shear force of the 100μm square resin layer on the copper substrate was measured using an adhesive strength tester (manufactured by XYZTEC, CondorSigma), and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion" column of Table 2. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. -Evaluation Criteria- A: The shear force exceeds 40gf. B: The shear force exceeds 35gf and is less than 40gf. C: The shear force exceeds 25gf and is less than 35gf. D: The shear force is less than 25gf. In addition, 1gf is 0.00980665N.

[Evaluation of reliability (metal adhesion after heating)] In each embodiment or comparative example, in the evaluation of the above-mentioned adhesion, after the resin layer was formed by heating at 230°C for 3 hours, the shear force was measured after the resin layer was placed in a constant temperature bath at 175°C for 1,000 hours. In addition, the metal adhesion after heating was evaluated according to the same evaluation method and evaluation criteria as the evaluation method in the above-mentioned adhesion evaluation. The evaluation results are shown in the "Reliability" column of Table 2. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film.

[Table 2] Preserve stability Adhesion reliability Embodiment 1 A A A Embodiment 2 B A A Embodiment 3 A A A Embodiment 4 B A A Embodiment 5 A B B Embodiment 6 A B B Embodiment 7 A B B Embodiment 8 A A A Embodiment 9 A A A Embodiment 10 A A A Embodiment 11 B A A Embodiment 12 B A A Embodiment 13 B A A Embodiment 14 A A A Embodiment 15 A A A Embodiment 16 A A A Embodiment 17 A A A Embodiment 18 A A A Embodiment 19 A A A Embodiment 20 A A A Embodiment 21 A A A Embodiment 22 A A A Embodiment 23 A A A Embodiment 24 A A A Embodiment 25 A A A Embodiment 26 A A A Embodiment 27 A A A Embodiment 28 A A A Embodiment 29 A A A Embodiment 30 A A A Embodiment 31 B C C Embodiment 32 A B B Embodiment 33 B B B Comparison Example 1 B D D Comparison Example 2 B D D

According to the above results, it can be seen that when the resin composition of the present invention containing at least one resin selected from the group including polyimide and polyimide precursor and containing the structure represented by formula (1-1) in the solid component is used, a cured film with excellent adhesion to the metal layer can be obtained. The comparative compositions described in Comparative Examples 1 to 3 do not contain the structure represented by formula (1-1) in the solid component. It can be seen that the cured film obtained by such a comparative composition has poor adhesion to the metal layer.

<Example 101> The resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 100°C for 5 minutes to form a resin composition layer with a film thickness of 20μm, and then exposed using a stepper (Nikon Co., Ltd., NSR1505 i6). The exposure was performed by irradiating light with 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 was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern. Then, the film was heated at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without.

Claims (12)

A resin composition comprising at least one resin selected from the group consisting of polyimide and a polyimide precursor, wherein the solid component comprises a structure represented by formula (1-1), wherein the molar amount of the structure represented by formula (1-1) is 0.015 mmol/g to 1.0 mmol/g relative to the total solid content of the resin composition,

In formula (1-1), ^R1 and ^R2 each independently represent a saturated aliphatic alkyl group having 3 to 6 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, ^X1 represents an oxygen atom or a sulfur atom, ^L1 represents -C(=O)- or -S(=O) _2- , * ¹ and * ² each independently represent a bonding site with other structures, and at least two of ^R1 , ^R2 , the structure bonded to * ¹ , and the structure bonded to * ² may bond to form a ring structure. The resin composition as described in claim 1, wherein the resin comprises the structure represented by the aforementioned formula (1-1). The resin composition as described in claim 1 or claim 2 further comprises a compound having a structure represented by the aforementioned formula (1-1) and different from the aforementioned resin. The resin composition as claimed in claim 1 or claim 2, comprising a structure represented by the following formula (1-2) as the structure represented by the aforementioned formula (1-1),

In formula (1-2), R ²¹ and R ²² each independently represent a saturated aliphatic alkyl group having 3 to 6 carbon atoms, or a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms, R ²³ represents a hydrogen atom, a saturated aliphatic alkyl group having 3 to 6 carbon atoms, or a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms, * represents a bonding site with other structures, and at least two of R ²¹ , R ²² , R ²³ and the structure bonded to * may bond to form a ring structure. The resin composition as described in claim 1 or claim 2 further comprises a photopolymerization initiator. The resin composition as described in claim 1 or claim 2 further comprises a crosslinking agent. The resin composition as described in claim 1 or claim 2 is used for forming an interlayer insulating film for a redistribution layer. A hardened film, which is formed by hardening the resin composition as described in any one of claim 1 to claim 7. A laminate having two or more layers of hardened films as described in claim 8, and having a metal layer between any of the aforementioned hardened films. A method for manufacturing a hardened film includes a film forming step, wherein the resin composition described in any one of claim 1 to claim 7 is applied to a substrate to form a film. The method for manufacturing a hardened film as described in claim 10 includes the step of heating the aforementioned film at 50°C to 450°C. A semiconductor device having a hardened film as described in claim 8.