WO2024048436A1

WO2024048436A1 - Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

Info

Publication number: WO2024048436A1
Application number: PCT/JP2023/030663
Authority: WO
Inventors: 大輔浅川; 友小澤
Original assignee: 富士フイルム株式会社
Priority date: 2022-08-30
Filing date: 2023-08-25
Publication date: 2024-03-07

Abstract

Provided are: a resin composition comprising at least one resin selected from the group consisting of cyclic resins and precursors thereof, and compound A corresponding to at least one of compound a1 and compound a2; a cured product; a laminate; a method for producing a cured product; a method for producing a laminate; a method for producing a semiconductor device; and a semiconductor device. Compound a1 has a protected primary amine structure and a specific structure. Compound a2 has a protected primary alkyl amine structure and a specific group.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.

BACKGROUND ART In modern times, resin materials manufactured from resin compositions containing resin are utilized in various fields.
For example, cyclized resins such as polyimide have excellent heat resistance and insulation properties, and are therefore used in a variety of applications. The above-mentioned uses are not particularly limited, but in the case of semiconductor devices for mounting, for example, they may be used as materials for insulating films and sealing materials, or as protective films. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing the cyclized resin or a precursor of the cyclized resin such as a polyimide precursor.
Such a resin composition is applied to a base material by coating, for example, to form a photosensitive film, and then, as necessary, exposure, development, heating, etc. are performed to form a cured product on the base material. be able to.
The precursor of the cyclized resin, such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
Since the resin composition can be applied by known coating methods, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when it is applied. It can be said that it has excellent characteristics. In addition to the high performance of cyclized resins such as polyimide, there are increasing expectations for the industrial application of the above-mentioned resin compositions due to their excellent manufacturing adaptability.

For example, Patent Document 1 describes at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a nonionic compound B, and a polymerizable compound and a photosensitive compound. The compound B includes a partial structure containing two or more nitrogen atoms and an electron-withdrawing group, and at least one of the nitrogen atoms in the partial structure contains at least one compound selected from the group consisting of: The distance 1 between two nitrogen atoms is 2 atoms or less, and the distance 2 between any of the nitrogen atoms for which the distance 1 is 2 atoms or less and the electron-withdrawing group is 1 atom or less. Curable resin compositions are described.
Patent Document 2 describes (A) a polyimide precursor; (B) having a plurality of amino groups protected with a group that can be deprotected by acid or base or heat, and having a molecular weight of 250 to 600; a base-protected compound in which the plurality of amino groups are aliphatic chain or alicyclic amino groups, and the solubility parameter value is 20.0 or more and 24.0 or less; and (C) a photopolymerization initiator. A negative-working photosensitive resin composition is described.

International Publication No. 2020/179671 International Publication No. 2019/107250

A resin composition for obtaining a cured product is required to have excellent adhesion to a substrate even after the resulting cured product is exposed to high-temperature conditions.

The present invention includes a resin composition that has excellent adhesion to a base material even after the obtained cured product is exposed to high temperature conditions, a cured product obtained by curing the above resin composition, and the above cured product. The present invention aims to provide a laminate, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.

Examples of representative embodiments of the invention are shown below.
<1> At least one resin selected from the group consisting of cyclized resins and precursors thereof;
A resin composition comprising a compound A corresponding to at least one of the following compound a1 and compound a2.
Compound a1: Protected primary amine structure, oxazole ring, thiazole ring, pyrimidine ring, Schiff base group, phenolic hydroxyl group, group represented by the following formula (1-1), the following formula (1-2) ) Compound a2 having at least one structure selected from the group consisting of a group represented by the following formula (1-4): a protected primary alkylamine structure, and Having a group represented by any of the following formulas (1-1) to (1-4)
In formula (1-1), X ¹ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ² to =N-, and when X ¹ is -C(R ^x ) ₂ - or -O-, at least two of X ² to X ⁷ represent =N-, and ^X ¹ is -NR When S-, at least one of X ² to X ⁷ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent and one of X ⁴ to X ⁷ contains R ^x which is a bonding site with another structure represented by *, and in the group represented by formula (1-1), There is only one R ^x which is a binding site with the structure.
In formula (1-2), X ¹⁴ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ⁸ to =N-, and when X ¹⁴ is -C(R ^x ) ₂ - or -O-, at least two of X ⁸ to X ¹³ represent =N-, and ^X ¹⁴ is -NR When S-, at least one of X ⁸ to X ¹³ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent , one of X ⁸ , X ¹³ and X ¹⁴ contains R ^x which is a bonding site with another structure represented by *, and in the group represented by formula (1-2), There is only one R ^x which is a binding site with another structure.
In formula (1-3), X ¹⁵ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ¹⁶ to =N-, and when X ¹⁵ is -C(R ^x ) ₂ - or -O-, at least two of X ¹⁶ to X ¹⁸ represent =N-, and ^X ¹³ is -NR When S-, at least one of X ¹⁶ to X ¹⁸ represents =N-, and R ^X each independently represents a hydrogen atom or a monovalent substituent.
In formula (1-4), X ¹⁹ to X ²⁶ each independently represents =CR ^X - or =N-, at least two of X ¹⁹ to X ²⁶ represent =N-, and ^R R represents a bonding site with another structure represented by *, a hydrogen atom or a monovalent substituent, and one of X ¹⁹ to X ²⁶ is a bonding site with another structure represented by * In the group represented by ^formula (1-4), there is only one R ^x which is a bonding site with another structure represented by *.
<2> The resin composition according to <1>, wherein the compound A is a compound that is decomposed by the action of light, heat, or a base to generate an aliphatic primary amine.
<3> The compound a1 is selected from the group consisting of a protected primary amine structure, a group represented by formula (1-1), and a group represented by formula (1-2). The resin composition according to <1> or <2>, which has at least one type of structure.
<4> The resin composition according to any one of <1> to <3>, wherein the compound A is a compound represented by the following formula (A-2) or formula (A-3).

In formula (A-2), R ⁷ each independently represents an alkyl group that may have a substituent, a plurality of R ⁷ may be combined to form a ring structure, and R ⁸ is represented by formula ( At least one structure selected from the group consisting of a group represented by any one of 1-1) to formula (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base, and a phenolic hydroxyl group. L ¹ represents a single bond or a divalent linking group.
In formula (A-3), R ⁹ is a group represented by any one of formulas (1-1) to (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base group, a phenolic hydroxyl group, represents an organic group having at least one type of structure selected from the group consisting of, and L ² represents a single bond or a divalent linking group.
<5> The resin composition according to any one of <1> to <4>, wherein the resin is polyimide or a polyimide precursor.
<6> The resin composition according to any one of <1> to <5>, further comprising an aromatic heterocyclic compound different from the compound A.
<7> The resin composition according to any one of <1> to <6>, further comprising a photopolymerization initiator and a polymerizable compound.
<8> The resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer.
<9> A cured product obtained by curing the resin composition according to any one of <1> to <8>.
<10> A laminate including two or more layers made of the cured product according to <9>, and a metal layer between any of the layers made of the cured product.
<11> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <8> onto a substrate to form a film.
<12> The method for producing a cured product according to <11>, comprising an exposure step of selectively exposing the film to light, and a development step of developing the film using a developer to form a pattern.
<13> The method for producing a cured product according to <11> or <12>, which includes a heating step of heating the film at 50 to 450°C.
<14> A method for producing a laminate, including the method for producing a cured product according to any one of <11> to <13>.
<15> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to any one of <11> to <13>.
<16> A semiconductor device comprising the cured product according to <9>.

According to the present invention, there is provided a resin composition that has excellent adhesion to a substrate even after the obtained cured product is exposed to high temperature conditions, a cured product obtained by curing the resin composition, and a cured product obtained by curing the resin composition. A laminate including the above, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.

Main embodiments of the present invention will be described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range expressed using the symbol "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit, respectively.
As used herein, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
In the description of a group (atomic group) in this specification, the description that does not indicate substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both "acrylate" and "methacrylate", or either "(meth)acrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl."
In this specification, Me in the structural 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. Further, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC), and are defined as polystyrene equivalent values. In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise stated, those molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, if THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in the GPC measurement.
In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the base material is referred to as "top", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "top". , the opposite direction is called "down". Note that such a setting in the vertical direction is for convenience in this specification, and in an actual embodiment, the "up" direction in this specification may be different from vertically upward.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise stated, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In this specification, combinations of preferred aspects are more preferred aspects.

(Resin composition)
The resin composition of the present invention includes at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound A that corresponds to at least one of the following compounds a1 and compound a2.
Compound a1: Protected primary amine structure, oxazole ring, thiazole ring, pyrimidine ring, Schiff base group, phenolic hydroxyl group, group represented by the following formula (1-1), the following formula (1-2) ) Compound a2 having at least one structure selected from the group consisting of a group represented by the following formula (1-4): a protected primary alkylamine structure, and Having a group represented by any of the following formulas (1-1) to (1-4)

In formula (1-1), X ¹ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ² to =N-, and when X ¹ is -C(R ^x ) ₂ - or -O-, at least two of X ² to X ⁷ represent =N-, and ^X ¹ is -NR When S-, at least one of X ² to X ⁷ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent and one of X ⁴ to X ⁷ contains R ^x which is a bonding site with another structure represented by *, and in the group represented by formula (1-1), There is only one R ^x that is a binding site with the structure.
In formula (1-2), X ¹⁴ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ⁸ to =N-, and when X ¹⁴ is -C(R ^x ) ₂ - or -O-, at least two of X ⁸ to X ¹³ represent =N-, and ^X ¹⁴ is -NR When S-, at least one of X ⁸ to X ¹³ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent , one of X ⁸ , X ¹³ and X ¹⁴ contains R ^x which is a bonding site with another structure represented by *, and in the group represented by formula (1-2), There is only one R ^x that is a binding site with other structures.
In formula (1-3), X ¹⁵ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ¹⁶ to =N-, and when X ¹⁵ is -C(R ^x ) ₂ - or -O-, at least two of X ¹⁶ to X ¹⁸ represent =N-, and ^X ¹³ is -NR When S-, at least one of X ¹⁶ to X ¹⁸ represents =N-, and R ^X each independently represents a hydrogen atom or a monovalent substituent.
In formula (1-4), X ¹⁹ to X ²⁶ each independently represents =CR ^X - or =N-, at least two of X ¹⁹ to X ²⁶ represent =N-, and ^R R represents a bonding site with another structure represented by *, a hydrogen atom or a monovalent substituent, and one of X ¹⁹ to X ²⁶ is a bonding site with another structure represented by * In the group represented by ^formula (1-4), there is only one R ^x which is a bonding site with another structure represented by *.

The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. preferable.
The resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and can be used for forming an interlayer insulating film for a rewiring layer. preferable.
In particular, it is one of the preferred embodiments of the present invention that the resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer.
Further, the resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to development in which non-exposed areas are removed by development during exposure and development, and positive development refers to development in which exposed areas are removed by development.
The above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method include, for example, the exposure method explained in the exposure step in the explanation of the method for producing a cured product, and the developer and development method explained in the development step. is used.

According to the resin composition of the present invention, a cured product having excellent adhesion to a substrate (particularly a metal substrate, particularly a copper substrate) can be obtained even after being exposed to high-temperature conditions.
Although the mechanism by which the above effects are obtained is unknown, it is assumed as follows.

The resin composition of the present invention contains at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound A having a specific structure.
The cured product obtained from the resin composition of the present invention has excellent adhesion to a substrate (particularly a metal substrate, particularly a copper substrate) even after being exposed to high temperature conditions.
Although the mechanism by which the above effects are obtained is not clear, it is presumed as follows.
A compound corresponding to compound a1 has a protected primary amine structure (Structure 1), a structure having a wide π conjugated plane, a structure having multiple nitrogen atoms, an oxygen atom or a sulfur atom, and a nitrogen atom. structure (Structure 2). When the protection in the primary amine structure is removed during curing by heating, etc., a compound containing the primary amine structure and the above structure 2 is generated. Here, structure 2 in the above compound and the resin have a strong interaction, and the primary amine structure or structure 2 and the base material have high adsorption properties, so the interaction between the resin and the compound a1 and the compound a1 - It is assumed that adsorption between the base materials provides excellent adhesion even after exposure to high temperature conditions.
The compound corresponding to compound a2 includes a protected primary alkylamine structure (Structure 3) and an azole structure (Structure 4) having at least two or more nitrogen atoms. When the protection in the primary alkylamine structure is removed during curing by heating, etc., a compound containing the primary alkylamine structure and the above structure 4 is generated. Here, the primary alkylamine structure in the compound and the resin react to form a covalent bond, and since the structure 4 and the base material have high adsorption properties, the interaction between the resin and the compound a2, It is presumed that adsorption between compound a2 and the base material provides excellent adhesion even after exposure to high temperature conditions.

Here, Patent Documents 1 and 2 do not describe a precursor of a cyclized resin and a composition containing Compound A.

Hereinafter, the components contained in the resin composition of the present invention will be explained in detail.

<Specific resin>
The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
In the present invention, the "main chain" refers to the relatively longest bond chain in the resin molecule, and the "side chain" refers to other bond chains.
Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like.
The precursor of cyclized resin refers to a resin that undergoes a chemical structure change due to external stimulation to become a cyclized resin. Preferably, a resin that undergoes a chemical structure change due to heat to become a cyclized resin, and that undergoes a ring-closing reaction due to heat. More preferred is a resin that becomes a cyclized resin by forming a ring structure.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, and the like.
That is, the resin composition contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. It is preferable.
It is preferable that the resin composition contains polyimide or a polyimide precursor as the specific resin.
It is preferable that the specific resin has a polymerizable group, and more preferably a radically polymerizable group.
When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer can be included if necessary. For example, a negative photosensitive film is formed from such a resin composition.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.

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

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

A ¹ and A ² in formula (2) each independently represent an oxygen atom or -NR ^z -, and preferably an oxygen atom.
^Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the above straight chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the above cyclic aliphatic group and aromatic group, the hydrocarbon group in the chain may be substituted with a hetero atom. may be substituted with a group containing. Examples of R ¹¹¹ in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, with a group represented by -Ar-L-Ar- being preferred. However, Ar is each independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO ₂ -, -NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. One type of diamine may be used, or two or more types may be used.
Specifically, R ¹¹¹ is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or any of these. A diamine containing a combination of groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the straight chain or branched aliphatic group mentioned above, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom.In the above cyclic aliphatic group and aromatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom. may be substituted with a group containing. Examples of groups containing aromatic groups include the following.

In the formula, A represents a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -C (= A group selected from O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof is preferable, and has a carbon number of 1 and may be substituted with a single bond or a fluorine atom. -3 alkylene groups, -O-, -C(=O)-, -S-, or -SO ₂ - is more preferable, and -CH ₂ -, -O-, - More preferably, it is S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.
In the formula, * represents a bonding site with another structure.

As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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'- or 3,3' -diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4 -aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4- aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4 -hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4- aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9, 10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) ) Benzene, 1,3-bis(4-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'-tetraamino diphenyl ether, 1,4-diaminoanthraquinone, 1,5- Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7 -Diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3- Bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-amino phenyl)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, selected from 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotridine and 4,4'-diaminoquaterphenyl At least one type of diamine is mentioned.

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

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

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

Further, from the viewpoint of 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 i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferable.
Formula (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoro It is a methyl group, and each * independently represents a bonding site with the nitrogen atom in formula (2).
The monovalent organic groups R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). represent.
Examples of the diamine giving 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, 4,4'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * each independently represents a bonding site with another structure.

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

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types of tetracarboxylic dianhydride residues as the structure corresponding to ^R115 .
It is preferable that the tetracarboxylic dianhydride is represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as the preferred range of R ¹¹⁵ in formula (2).

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3' , 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , 7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these Examples include alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ includes a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Moreover, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. It will be done. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group. , (meth)acryloyloxy group, a group represented by the following formula (III), and the like, with the group represented by the following formula (III) being preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1, Examples include 3-butanediyl group, -CH ₂ CH (OH) CH ₂ -, polyalkyleneoxy group, alkylene groups such as ethylene group and propylene group, -CH ₂ CH (OH) CH ₂ -, cyclohexyl group, polyalkylene group. An oxy group is more preferred, and an alkylene group such as an ethylene group or a propylene group, or a polyalkyleneoxy group is even more preferred.
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or an arrangement having blocks. Alternatively, an arrangement having an alternating pattern or the like may be used.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferable, 2 to 5 is even more preferable, 2 to 4 is even more preferable, 2 or 3 is even more preferable, and 2 is particularly preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
Further, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
From the viewpoint of solvent solubility and solvent resistance, polyalkyleneoxy groups include polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or multiple ethyleneoxy groups and multiple propyleneoxy groups. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable. In the above-mentioned group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in an alternating pattern. Preferred embodiments of the repeating number of ethyleneoxy groups, etc. in these groups are as described above.

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

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but examples include an acetal group, a ketal group, a silyl group, and a silyl ether group. , a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
Specific examples of acid-decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group. group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group is preferred.

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

Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include embodiments in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used as the diamine.

The amount of carboxyl groups in the polyimide precursor is preferably 0.05 to 0.30 mmol/g, more preferably 0.10 to 0.25 mmol/g.
Further, the esterification rate (the molar amount of carboxy ester relative to the total molar amount of carboxy groups and carboxy ester) in the polyimide precursor is preferably 90% or more, more preferably 95% or more, and 98% or more. The upper limit of the esterification rate is not particularly limited, and may be 100% or less.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the exposure latitude.
Formula (2-A)

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

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

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

An embodiment of the polyimide precursor in the present invention includes an embodiment in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the degree of molecular weight dispersion of the polyimide precursor is not particularly determined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In this specification, the molecular weight dispersity is a value calculated from weight average molecular weight/number average molecular weight.
When the resin composition contains multiple types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are each within the above ranges.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23°C in 100 g of a 2.38% by mass tetramethylammonium aqueous solution, and from the perspective of pattern formation, 0.5 g or more. The polyimide is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. The upper limit of the amount dissolved is not particularly limited, but is preferably 100 g or less.
The polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of film strength and insulation properties of the organic film obtained.

-Fluorine atom-
From the viewpoint of the film strength of the organic film obtained, it is also preferable that the polyimide has a fluorine atom.
The fluorine atom is preferably included in, for example, R ¹³² in the repeating unit represented by formula (4) described later or R 131 in the repeating unit represented by formula (4) described later, and is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later. It is more preferable that R ¹³² in the repeating unit represented by formula (4) or R ¹³¹ in the repeating unit represented by formula (4) described below be included as a fluorinated alkyl group.
The amount of fluorine atoms based on the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms.
The silicon atom is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later. ) More preferably, it is included as a siloxane structure.
The silicon atom or the organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.
The amount of silicon atoms based on the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

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

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

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, the number of repeating alkyleneoxy groups is 1 to 12) is preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a combination of two or more of these.
The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.

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

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group combining two or more of these; represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with the oxygen atom to which R ²¹ in formula (IV) is bonded.
In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R ²¹ in formula (IV). The preferred embodiments are the same as the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) includes, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained by, for example, reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.

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

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g.

- Polymerizable groups other than groups having ethylenically unsaturated bonds -
The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
A polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described below, for example.
The amount of polymerizable groups other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and preferably 0.001 to 0.05 mol/g. More preferred.

-Polar conversion 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 explained for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiments are also the same.
The polarity converting group is contained, for example, in R ¹³¹ and R ¹³² in the repeating unit represented by formula (4) described below, the terminal of polyimide, and the like.

-Acid value-
When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more. It is more preferable that
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
When polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, more preferably 2 to 30 mgKOH/g. Preferably, 5 to 20 mgKOH/g is more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably an acid group having a pKa of 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this specification, pKa is a value calculated by ACD/ChemSketch (registered trademark) unless otherwise specified. For pKa, the value published in "Revised 5th Edition Chemistry Handbook Basic Edition" edited by the Chemical Society of Japan may be referred to.
When the acid group is a polyhydric acid such as phosphoric acid, the above pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

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

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).

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

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

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).

Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, or a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include those similar to R ¹¹¹ in formula (2), and the preferred ranges are also the same.
Examples of R ¹³¹ include diamine residues remaining after removal of the amino group of diamine. Examples of diamines include aliphatic, cycloaliphatic, and aromatic diamines. A specific example is R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in its main chain in order to more effectively suppress the occurrence of warpage during firing. More preferred are diamine residues containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferred are diamine residues containing no aromatic ring among the above diamines. It is.

Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. 1-(2-(2-(2-aminopropoxy)ethoxy) Examples include, but are not limited to, propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include those similar to R ¹¹⁵ in formula (2), and the preferred ranges are also the same.
For example, four bonds of a tetravalent organic group exemplified as R ¹¹⁵ combine with four -C(=O)- moieties in formula (4) to form a condensed ring.

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

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

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

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

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

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

The polyimide may include repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R ¹³¹ and R ¹³² , or two or more repeating units with different combinations of R ¹³¹ and R ¹³² . The repeating unit represented by the above formula (4) may be included. In addition to the repeating unit represented by the above formula (4), the polyimide may contain other types of repeating units. Other types of repeating units include, for example, the repeating unit represented by the above formula (2).

Polyimide can be produced, for example, by reacting tetracarboxylic dianhydride and diamine (partly replaced with an acid anhydride) at low temperature; A method of reacting a diester with a diamine (substituted with an end-capping agent that is a compound or a monoacid chloride compound or a monoactive ester compound) with a diamine, and a diester is obtained with a tetracarboxylic dianhydride and an alcohol, and then a diamine (partly of which is a monoamine) is reacted with a diamine. A diester is obtained by reacting tetracarboxylic dianhydride and alcohol in the presence of a condensing agent, and then the remaining dicarboxylic acid is converted into an acid chloride, and a diamine (some of which is substituted with a monoamine) is reacted with a condensing agent. A polyimide precursor is obtained using a method such as reacting with a terminal capping agent), and this is completely imidized using a known imidization reaction method, or an imidization reaction is performed during the process. It can be synthesized by stopping the polymer and introducing a partial imide structure, or by blending a fully imidized polymer with its polyimide precursor to introduce a partial imide structure. . Further, other known polyimide synthesis methods can also be applied.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, even more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The molecular weight dispersity of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the degree of dispersion of the molecular weight of polyimide is not particularly determined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
When the resin composition contains multiple types of polyimides as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by considering the plurality of types of polyimides as one resin are each within the above ranges.

[Polybenzoxazole precursor]
Examples of the polybenzoxazole precursor include compounds described in paragraphs 0073 to 0095 of International Publication No. 2022/145355. The above description is incorporated herein.

[Polybenzoxazole]
Examples of the polybenzoxazole include compounds described in paragraphs 0096 to 0103 of International Publication No. 2022/145355. The above description is incorporated herein.

[Polyamideimide precursor]
Examples of the polyamide-imide precursor include compounds described in paragraphs 0104 to 0119 of International Publication No. 2022/145355. The above description is incorporated herein.

[Polyamideimide]
Examples of the polyamideimide include compounds described in paragraphs 0120 to 0133 of International Publication No. 2022/145355. The above description is incorporated herein.

[Method for producing polyimide precursor, etc.]
For example, polyimide precursors can be obtained by reacting tetracarboxylic dianhydride and diamine at low temperature, by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid, and by using a condensing agent or an alkylating agent. A method of esterifying using a tetracarboxylic dianhydride and an alcohol, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine in the presence of a condensing agent, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, The remaining dicarboxylic acid can then be acid-halogenated using a halogenating agent and reacted with a diamine. Among the above production methods, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated using a halogenating agent and reacted with a diamine is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
In the method for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one or two or more.
The organic solvent can be determined as appropriate depending on the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. is exemplified.
In the method for producing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The number of basic compounds may be one or two or more.
The basic compound can be determined as appropriate depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Examples include pyridine.

-Terminal sealing agent-
In the production method of polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as the polyimide precursor. When sealing carboxylic acid anhydride and acid anhydride derivatives remaining at the end of the resin, examples of the terminal capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. From the viewpoint of properties, it is more preferable to use monoalcohols, phenols, and monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, secondary alcohols such as 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 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. can be mentioned. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents.
Furthermore, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group that can react with the amino group. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. can be mentioned. Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantane carbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.

-Solid precipitation-
The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbed by-products of the dehydration condensation agent coexisting in the reaction solution, the obtained product is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof. By introducing a polymer component and precipitating the polymer component, a polyimide precursor or the like can be obtained by depositing the polymer component as a solid and drying it. In order to improve the degree of purification, operations such as redissolving the polyimide precursor, reprecipitation, drying, etc. may be repeated. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

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

It is also preferable that the resin composition of the present invention contains at least two types of resin.
Specifically, the resin composition of the present invention may contain a total of two or more types of specific resin and other resins described below, or may contain two or more types of specific resin, but may contain a specific resin. It is preferable to include two or more types.
When the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)) Preferably, a precursor is included.

<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. etc.
For example, by further adding a (meth)acrylic resin, a resin composition with excellent coating properties can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described below, a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups contained in 1 g of resin) may be used. By adding a (meth)acrylic resin (having a concentration of 1×10 ⁻³ mol/g or more) to a resin composition, it is possible to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can.

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

<Compound A>
The resin composition of the present invention contains Compound A.
Compound A is a compound corresponding to at least one of compound a1 and compound a2 below.
Compound a1: Protected primary amine structure, oxazole ring, thiazole ring, pyrimidine ring, Schiff base group, phenolic hydroxyl group, group represented by formula (1-1), formula (1-2) Compound a2 having at least one type of structure (hereinafter also referred to as "specific structure a1") selected from the group consisting of the group represented by the formula (1-4) and the group represented by the formula (1-4): It has a primary alkylamine structure and a group represented by any one of formulas (1-1) to (1-4).

[Compound a1]
In the present invention, the primary amine structure refers to a structure in which one hydrogen atom out of three hydrogen atoms of ammonia is substituted with an organic group.
In the present invention, a protected primary amine structure refers to a structure in which one of the hydrogen atoms of the primary amine structure is bonded to a protecting group.
Compound a1 may have only one protected primary amine structure, or may have two or more protected primary amine structures. The number of protected primary amine structures in compound a1 is preferably 1 to 4, more preferably 1 or 2. Furthermore, an embodiment in which there is only one protected primary amine structure is also one of the preferred embodiments of the present invention.
The above-mentioned protecting group is not particularly limited and includes known protecting groups for amino groups, such as tertiary alkyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl (Fmoc) group, or the following formula (P- A group represented by 1) is preferable, a tertiary alkyloxycarbonyl group or an Fmoc group is more preferable from the viewpoint of solubility of the compound itself, and a tertiary alkyloxycarbonyl group or an Fmoc group is more preferable from the viewpoint of chemical resistance of the obtained cured product. More preferred is a class alkyloxycarbonyl group.
In the present invention, the tertiary alkyl group in the tertiary alkyloxycarbonyl group refers to a group having a structure in which three carbon atoms are bonded to the carbon atom at the bonding point. The bonding point of a tertiary alkyl group refers to the atom at the position where the tertiary alkyl group is bonded to another structure. A carbon atom that is directly bonded without a linking group.

In formula (P-1), L ¹ represents a hydrocarbon group, and * represents a bonding site with the nitrogen atom to be protected in the primary amine structure to be protected.
^L1 is preferably a group containing at least an aromatic hydrocarbon group, more preferably a group formed by a combination of an aromatic hydrocarbon group and a saturated aliphatic hydrocarbon group, and preferably a group having the following structure. More preferred. In the structure below, * represents a bonding site with a nitrogen atom in the primary amine structure to be protected, and # represents a bonding site with a hydroxy group in formula (P-1).

The oxazole ring, thiazole ring, and pyrimidine ring may further have a fused ring. The condensed ring is preferably an aromatic 6-membered ring structure, and more preferably a benzene ring, pyrimidine ring, pyrazine ring, or pyrimidine ring.

The Schiff base group refers to a group represented by the following formula (S-1).

In formula (S-1), * represents a bonding site with a carbon atom, preferably a bonding site with a hydrocarbon group.

Preferred embodiments of the group represented by formula (1-1) and the group represented by formula (1-2) will be described later.

Compound a1 is a substituent for a hydrogen atom in a hydrocarbon group that has specific structure a1 directly bonded to the nitrogen atom in the protected primary amine structure, or is bonded to the nitrogen atom in the protected primary amine structure. It is preferable that the specific structure a1 be a bonded structure.
The hydrocarbon group is preferably an alkyl group whose hydrogen atom may be further substituted with a substituent different from the specific structure a1.
Preferred embodiments of the protecting group are the same as those for compound a1.

When the specific structure a1 is bonded as a substituent for a hydrogen atom in a hydrocarbon group, the hydrocarbon group and the specific structure a1 may be bonded via a linking group. The linking group is not particularly limited, but examples include -O-, -NR ^N -, and the like. Preferred embodiments of R ^N are as described above.

From the viewpoint of adhesion after being exposed to high temperature conditions, compound a1 has a group represented by formula (1-1) and a group represented by formula (1-2) among specific structures a1. It is preferable that at least one structure selected from the group consisting of:

[Compound a2]
Compound a2 is a compound having a protected primary alkylamine structure and a group represented by any of the following formulas (1-1) to (1-4).
In the present invention, the primary alkylamine structure refers to a structure in which one hydrogen atom out of three hydrogen atoms of ammonia is substituted with an alkyl group. The hydrogen atom in the above alkyl group is a group represented by any one of formulas (1-1) to (1-4), or a group represented by any one of formulas (1-1) to (1-4). is preferably substituted with a group containing a group represented by formula (1-1) to formula (1-4). Furthermore, the hydrogen atom in the alkyl group may be further substituted with another substituent as long as the effects of the present invention can be obtained.
Compound a2 may have only one protected primary alkylamine structure, or may have two or more protected primary alkylamine structures. The number of protected primary alkylamine structures in compound a2 is preferably 1 to 4, more preferably 1 or 2. Furthermore, an embodiment in which there is only one protected primary alkylamine structure is also one of the preferred embodiments of the present invention.

In formula (1-1), X ¹ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ² to =N-, and when X ¹ is -C(R ^x ) ₂ - or -O-, at least two of X ² to X ⁷ represent =N-, and ^X ¹ is -NR When S-, at least one of X ² to X ⁷ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent and one of X ⁴ to X ⁷ contains R ^x which is a bonding site with another structure represented by *, and in the group represented by formula (1-1), There is only one R ^x which is a binding site with the structure.
In formula (1-2), X ¹⁴ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ⁸ to =N-, and when X ¹⁴ is -C(R ^x ) ₂ - or -O-, at least two of X ⁸ to X ¹³ represent =N-, and ^X ¹⁴ is -NR When S-, at least one of X ⁸ to X ¹³ represents =N-, and each R ^X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent , one of X ⁸ , X ¹³ and X ¹⁴ contains Rx which is a binding site with another structure represented by *, and in the group represented by formula (1-2), There is only one Rx, which is a binding site with another structure.
In formula (1-3), X ¹⁵ represents -C(R ^x ) ₂ -, -NR ^x -, -S-, or ^-O- , and ^X ¹⁶ to =N-, and when X ¹⁵ is -C(R ^x ) ₂ - or -O-, at least two of X ¹⁶ to X ¹⁸ represent =N-, and ^X ¹³ is -NR When S-, at least one of X ¹⁶ to X ¹⁸ represents =N-, and R ^X each independently represents a hydrogen atom or a monovalent substituent.
In formula (1-4), X ¹⁹ to X ²⁶ each independently represents =CR ^X - or =N-, at least two of X ¹⁹ to X ²⁶ represent =N-, and ^R R represents a bonding site with another structure represented by *, a hydrogen atom or a monovalent substituent, and one of X ¹⁹ to X ²⁶ is a bonding site with another structure represented by * In the group represented by ^formula (1-4), there is only one R ^x which is a bonding site with another structure represented by *.

In formula (1-1), X ¹ is preferably -NR ^x -, more preferably -NH-.
In formula (1-1), X ² is preferably =N-. .
In formula (1-1), X ³ is preferably =N-.
In formula (1-1), X ⁴ is preferably =N-.
In formula (1-1), X ⁵ is preferably =CR ^x -, more preferably =CH-.
In formula (1-1), X ⁶ is preferably =N-.
In formula (1-1), X ⁷ is preferably =CR ^X -.
^Rx , which is a binding site with another structure represented by *, is preferably present at ^X7 .
In formula (1-1), when X ¹ is -NR ^X - or ^-S- , it is preferable that at least two of X ² to X ⁷ represent = ^N- ; More preferably, three represent =N-.
In formula (1-1), R ^X is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

In formula (1-2), X ¹⁴ is preferably -O- or -S-, more preferably -S-.
In formula (1-2), X ⁸ is preferably =N-.
In formula (1-2), X ⁹ is preferably =CH- or =N-, more preferably =N-.
In formula (1-2), X ¹⁰ is preferably =CR ^x -, more preferably =CH-.
In formula (1-2), X ¹¹ is preferably =CR ^x -, more preferably =CH-.
In formula (1-2), X ¹² is preferably =CH- or =N-, more preferably =N-.
In formula (1-2), X ¹³ is preferably =CR ^X -.
R ^x , which is a binding site with another structure represented by *, is preferably present at X ¹³ .
In formula (1-2), R ^X is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

In formula (1-3), X ¹⁵ is -NR ^X - and all of X ¹⁵ to X ¹⁸ are =N-, or X ¹⁵ is -S- and X ¹⁶ is = It is preferable that it is N-, and X ¹⁷ and X ¹⁸ are =CR ^X -.
In formula (1-3), R ^X is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

In formula (1-4), preferably 2 to 5 of X ¹⁹ to X ²⁶ represent =N-, more preferably 2 to 4 of X ¹⁹ to X ²⁶ represent =N-, It is further preferred that two or three of ¹⁹ to X ²⁶ represent =N-.
In formula (1-4), X ¹⁹ is preferably =CR ^X -.
R ^x , which is a binding site with another structure represented by *, is preferably present at X ¹⁹ .
In formula (1-4), preferably 2 to 5 of X ²⁰ to X ²⁶ represent =N-, and more preferably 2 to 4 of X ¹⁹ to X ²⁶ represent =N-, It is further preferred that two or three of X ¹⁹ to X ²⁶ represent =N-.

[Primary amine]
Compound A is preferably a compound that decomposes under the action of light, heat, or a base to generate a primary amine. More preferably, it is a compound that decomposes upon action to generate an aliphatic primary amine.
The decomposition described above is preferably removal of a protecting group (deprotection).
In the present invention, the primary amine refers to a compound in which one hydrogen atom out of three hydrogen atoms of ammonia is substituted with an organic group.
Moreover, an aliphatic primary amine refers to a compound in which one hydrogen atom out of three hydrogen atoms of ammonia is substituted with an aliphatic group. The hydrogen atom in the above aliphatic group may be substituted with another structure.
When compound A is a compound that generates an aliphatic primary amine, the hydrogen atom in the aliphatic group is substituted with a group containing the above-mentioned specific structure a1 or a group represented by formula (1-3). It is preferable that the substituent is substituted with a group represented by the above-mentioned specific structure a1 or formula (1-3).

Whether Compound A decomposes under the action of light and generates a primary amine (preferably an aliphatic primary amine) can be confirmed by the following method.
Composition A was prepared by dissolving compound A in a solvent, and after irradiating it with light with a wavelength of 190 to 800 nm for 30 seconds at an exposure intensity of 25 W/cm ² under 1 atm and 25°C, HPLC ( If the amount of decomposition is determined by a method such as high-performance liquid chromatography and 0.01 mol% or more of primary amine is generated based on the total molar amount of Compound A, Compound A is converted into a primary amine by the action of light. is determined to occur. The amount of the primary amine generated is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. The upper limit of the amount of the primary amine generated is not particularly limited, but may be, for example, 1000 mol% or less.
When the resin composition contains a solvent, the concentration of compound A in the composition A is the same as the concentration in the resin composition, and the type of solvent in the composition is the same as the solvent contained in the resin composition. It can be done. Further, when the resin composition does not contain a solvent, the concentration of compound A in composition A can be about 1.0% by mass with respect to the total mass of composition A, and the solvent type is N-methyl- 2-pyrrolidone and the like can be used.

When compound A is decomposed by the action of heat to generate a primary amine (preferably an aliphatic primary amine), it is preferable to generate the primary amine by heating at 250°C, and by heating at 220°C. It is more preferable to generate a primary amine, it is even more preferable to generate a primary amine by heating at 200°C, it is particularly preferable to generate a primary amine by heating at 190°C, and it is particularly preferable to generate a primary amine by heating at 180°C. Most preferably, the primary amine is generated by. The lower limit of the temperature at which the primary amine is generated is not particularly limited, but from the viewpoint of storage stability of the composition, it is preferably, for example, 100° C. or higher.
Whether or not a certain compound A generates a primary amine at a certain temperature of X° C. is determined by the following method.
After heating 1 mole of Compound A in a closed container under 1 atmosphere at the above-mentioned temperature of If the primary amine is generated, it is determined that Compound A generates a primary amine upon heating at X°C. Whether or not the generated compound is a primary amine is confirmed, for example, by using ¹ H-NMR.
The amount of the primary amine generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of the primary amine generated is not particularly limited, but may be, for example, 1000 mol or less.

When compound A generates a primary amine (preferably an aliphatic primary amine) by the action of a base, compound A has a structure in which the primary amine structure is protected by a base-decomposable protecting group. It is preferable.
As the base-decomposable protecting group, for example, known protecting groups for amino groups that can be deprotected with a base can be used. As a group in which a primary amine is protected by such a protecting group, a group having a carbamate structure is preferable, and examples include a 9-fluorenylmethyl carbamate group, a 1,1-dimethyl-2-cyanomethyl carbamate group, and a para-nitromethyl carbamate group. A benzyl carbamate group or a 2,4-dichlorobenzyl carbamate group is more preferred.
Further, when Compound A has a structure that generates a primary amine under the action of a base, Compound A may also be a compound that generates a primary amine under the action of heat.
Whether Compound A generates a primary amine by the action of a base can be determined by the following method.
The determination is made by adding a basic compound to a solution of compound A and then titrating to measure the amine value.
Specifically, composition A is prepared by dissolving compound A in a solvent, and piperidine or triethylamine is added to composition A at 1 mol/L under 1 atm and 25°C to dissolve compound A. If 0.01 mol % or more of primary amine is generated based on the total molar amount, it is determined that Compound A generates a primary amine due to the action of a base. The amount of the primary amine generated is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. The upper limit of the amount of the primary amine generated is not particularly limited, but may be, for example, 1000 mol% or less. The amount of the primary amine generated can be measured by titration using a known method to determine the amine value.
When the resin composition contains a solvent, the concentration of compound A in the composition A is the same as the concentration in the resin composition, and the type of solvent in the composition is the same as the solvent contained in the resin composition. It can be done. Further, when the resin composition does not contain a solvent, the concentration of compound A in composition A can be about 1.0% by mass with respect to the total mass of composition A, and the solvent type is N-methyl- 2-pyrrolidone and the like can be used.

The primary amine generated from compound A preferably contains the above-mentioned specific structure a1 or a group represented by formula (1-3).
Specific examples of primary amines generated from compound A are shown below, but the present invention is not limited thereto.

[Compound represented by formula (A-1)]
Compound A is preferably a compound represented by the following formula (A-1).

In formula (A-1), R ^A is a group represented by any one of formulas (1-1) to (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base group, and a phenolic group. represents an organic group having at least one type of structure selected from the group consisting of a hydroxyl group, ^LA represents a single bond or a divalent linking group, and R ^P represents a protecting group for an amino group.

In formula (A-1), R ^A is preferably a group having the above specific structure a1 or a group represented by formula (1-3); It is also preferable that it is a group represented by:
Among these, R ^A is a group represented by formula (1-1), a group represented by formula (1-2), a group represented by formula (1-3), or a group representing these groups. It is preferably a group having the formula (1-1), a group represented by the formula (1-2), or a group represented by the formula (1-3).

In formula (A-1), L ^A is preferably a single bond, an alkyleneoxy group, or an alkyleneimino group, and a single bond, an alkyleneoxy group having 2 to 10 carbon atoms, or an alkyleneimino group having 2 to 10 carbon atoms. is more preferred, a single bond, an alkyleneoxy group having 2 to 4 carbon atoms, or an alkyleneimino group having 2 to 4 carbon atoms is even more preferred, and a single bond, an ethyleneoxy group, or an ethyleneimino group is particularly preferred. In the present invention, an alkyleneoxy group is a group represented by -RO-, an alkyleneimino group is a group represented by -RN(R ^N )-, and R represents an alkylene group. , R ^N are as described above.
Further, when L ^A is an alkyleneoxy group, it is preferable that the oxygen atom contained in the alkyleneoxy group and R ^A in formula (A-1) bond directly without using a linking group. When L ^A is an alkylene imino group, it is preferable that the nitrogen atom contained in the alkylene imino group and R ^A in formula (A-1) bond directly without using a linking group.

R ^P represents a protecting group for an amino group described in formula (A-1). The protecting group is not particularly limited and includes known protecting groups for amino groups, but a tertiary alkyloxycarbonyl group, an Fmoc group, or a group represented by the above formula (P-1) is preferred; A tertiary alkyloxycarbonyl group or an Fmoc group is more preferred, and a tertiary alkyloxycarbonyl group is even more preferred.

[Compound represented by formula (A-2) or formula (A-3)]
Compound A is preferably a compound represented by the following formula (A-2) or formula (A-3).

In formula (A-2), R ⁷ each independently represents an alkyl group that may have a substituent, a plurality of R ⁷ may be combined to form a ring structure, and R ⁸ is represented by formula ( At least one type selected from the group consisting of a group represented by any one of 1-1) to formula (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base, and a phenolic hydroxyl group. represents an organic group having a structure, and L ¹ represents a single bond or a divalent linking group.
In formula (A-3), R ⁹ is a group represented by any one of formulas (1-1) to (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base group, and a phenolic group. It represents an organic group having at least one type of structure selected from the group consisting of hydroxyl groups, and L ² represents a single bond or a divalent linking group.

In formula (A-2), R ⁷ is each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. More preferred.
In formula (A-2), the ring structure formed by combining a plurality of R ^7s is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure, and even more preferably a cyclopentane ring.
Preferred embodiments of L ¹ and R ⁸ in formula (A-2) are the same as those of L ^A and R ^A in formula (A-1), respectively.
Preferred embodiments of L ² and R ⁹ in formula (A-3) are the same as those of L ^A and R ^A in formula (A-1), respectively.

[Molecular weight]
The molecular weight of compound A is preferably 180 to 2,000, more preferably 200 to 1,000, and even more preferably 220 to 800.

[Synthesis method]
Compound A can be synthesized, for example, by the method described in Examples below. Further, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

〔Concrete example〕
Specific examples of compound A include, but are not limited to, F-1 to F-20 used in Examples.

〔Content〕
The content of compound A based on the total solid content of the resin composition of the present invention is preferably 0.01 to 10% by mass. The lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 4% by mass or less.
One type of compound A may be used alone, but two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount falls within the above range.
Further, in the resin composition of the present invention, the content of compound A relative to 100 parts by mass of the specific resin is preferably 0.05 to 8 parts by mass, more preferably 0.10 to 5 parts by mass.

<Organometallic complex>
The resin composition of the present invention may contain an organometallic complex from the viewpoint of chemical resistance.
The organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom, but it is preferably a complex compound containing a metal atom and an organic group, and a compound in which an organic group is coordinated to a metal atom. are more preferred, and metallocene compounds are even more preferred.
The metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands.
The organic group is not particularly limited, but preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable.
At least one of the above organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The above-mentioned cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
As the 5-membered cyclic group, a cyclopentadienyl group is preferred.
The organometallic complex preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but it is preferably a metal that falls under Group 4 elements, and more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium. Preferably, at least one metal selected from the group consisting of titanium and zirconium is more preferable, and titanium is particularly preferable.

The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or it may contain two or more kinds of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and even more preferably a titanocene compound or a zirconocene compound. , titanocene compounds are particularly preferred.

It is also preferable that the organometallic complex has the ability to initiate photoradical polymerization.
In the present invention, having the ability to initiate photoradical polymerization means being able to generate free radicals that can initiate radical polymerization by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and in which the radical cross-linker does not absorb light, radicals By checking whether the crosslinking agent disappears, it is possible to check whether the photoradical polymerization initiation ability exists. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical crosslinking agent, and for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and preferably a titanocene compound or a zirconocene compound. are more preferred, and titanocene compounds are particularly preferred.
When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex contains at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds. It is preferable that the compound is a type of compound, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, and at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds. More preferably, it is a species compound, and particularly preferably a titanocene compound.

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

As the organometallic complex, a compound represented by the following formula (P) is preferably mentioned.

In formula (P), M is a metal atom, and each R is independently a substituent.
Preferably, each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

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

Specific examples of organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis (η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following compounds may be mentioned.

Also included are the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738, the contents of which are incorporated herein.

The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
One type or two or more types of organometallic complexes can be used. When two or more types are used, the total amount is preferably within the above range.

<Polymerizable compound>
It is preferable that the resin composition of the present invention contains a polymerizable compound.
Here, it is also preferable that the resin composition of the present invention contains a photopolymerization initiator and a polymerizable compound, which will be described later.
Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[Radical crosslinking agent]
It is preferable that the resin composition of the present invention contains a radical crosslinking agent.
A radical crosslinking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinyl phenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferable, and from the viewpoint of reactivity, (meth)acryloyl group is more preferable.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and more preferably a compound having 2 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. It is also preferable.

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 radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and furthermore, halogen groups Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as or tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid mentioned above is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like. As a specific example, the descriptions in paragraphs 0113 to 0122 of JP-A No. 2016-027357 can be referred to, and the contents thereof are incorporated into the present specification.

The radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of the compound having a boiling point of 100° C. or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021/112189. This content is incorporated herein.

Preferred radical crosslinking agents other than those mentioned above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. This content is incorporated herein.

Examples of radical crosslinking agents include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320 (made by Nippon Kayaku Co., Ltd.) Co., Ltd.), A-TMMT (Shin Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and these (meth)acryloyl groups are ethylene glycol residues or A structure in which they are linked via a propylene glycol residue is preferred. These oligomeric types can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, which is a tetrafunctional acrylate with four ethyleneoxy chains, and SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.). (manufactured by Nippon Kayaku Co., Ltd.), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers. Certain UAS-10, UAB-140 (all manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin-Nakamura Chemical Industries) ), 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.), Blenmar PME400 (manufactured by NOF Corporation).

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

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. A radical crosslinking agent having the following is more preferable. Particularly preferably, in the radical crosslinking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will have excellent handling properties during production and excellent developability. Moreover, it has good polymerizability. The above acid value is measured in accordance with the description of JIS K 0070:1992.

It is preferable to use bifunctional methacrylate or acrylate as the resin composition from the viewpoint of pattern resolution and film stretchability.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, and PEG 600 diacrylate. Methacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol Diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, bisphenol EO adduct dimethacrylate of A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. These can be used as a mixture of two or more types, if necessary.
Note that, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of polyethylene glycol chains is about 200.
In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage of the pattern (cured product). Examples of monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and cyclohexyl (meth)acrylate. (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure.
In addition, examples of the radical crosslinking agent having two or more functional groups include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When containing a radical crosslinking agent, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

One type of radical crosslinking agent may be used alone, or a mixture of two or more types may be used. When two or more types are used together, it is preferable that the total amount falls within the above range.

[Other crosslinking agents]
It is also preferable that the resin composition of the present invention contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
Other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, and the above-mentioned photoacid generators or photobase generators are photosensitive to other compounds in the composition or their reaction products. It is preferable that the compound has a plurality of groups in its molecule that promote the reaction of forming a covalent bond between the compounds, and the reaction of forming a covalent bond with other compounds in the composition or the reaction products thereof is preferably Compounds having multiple groups in the molecule that are promoted by the action of acids or bases are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022/145355. The above description is incorporated herein.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
The photopolymerization initiator is preferably a radical photopolymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferable. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

The photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). It is preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, Examples include metallocene compounds, organic boron compounds, iron arene complexes, and the like. For these details, the descriptions in paragraphs 0165 to 0182 of JP2016-027357A and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated herein. In addition, compounds described in paragraphs 0065 to 0111 of JP 2014-130173, Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiators described in JP-A No. 2019-044030, the peroxide-based initiators described in JP-A No. 2019-167313, and the contents of these are Incorporated into the specification.

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

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the content of which is herein incorporated by reference. Incorporated.

Examples of α-hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DA ROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (manufactured by BASF) can be used.

Examples of α-aminoketone initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369. , and IRGACURE 379 (manufactured by BASF) can be used.

As the aminoacetophenone initiator, the acylphosphine oxide initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be suitably used. This content is incorporated herein.

More preferred examples of the photoradical polymerization initiator include oxime compounds. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A 2000-080068, compounds described in JP-A 2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017 /051680, compounds described in JP 2017-198865, compounds described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, compounds described in International Publication No. 2013/167515, etc. , the contents of which are incorporated herein.

Preferred oxime compounds include, for example, compounds with the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. Can be mentioned. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound used as a photoradical polymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.

Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). Radical photopolymerization initiator 2) described in the publication, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831, and Adeka Arcles NCI- 930 (manufactured by ADEKA Co., Ltd.), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Moreover, oxime compounds having the following structures can also be used.

Examples of the photoradical polymerization initiator include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring. Compounds, oxime compounds having a fluorine atom can also be used.
Furthermore, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, and an oxime compound having a substituent having a hydroxy group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 may be used. You can also do it. Their contents are incorporated herein.

As the photopolymerization initiator, it is also possible to use an oxime compound having an aromatic ring group Ar ^OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring. Examples of the electron-withdrawing group possessed by the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, An acyl group and a nitro group are preferred, an acyl group is more preferred because a film with excellent light resistance can be easily formed, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.

The oxime compound OX is preferably at least one selected from a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). preferable.

In the formula, ^R group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group,
^R Represents a sulfonyl group, acyloxy group or amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, R ^X12 is preferably an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600, the contents of which are incorporated herein.

Particularly preferable oxime compounds include oxime compounds having a specific substituent group as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061. Incorporated herein.

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

Further, the photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred.

As the photoradical polymerization initiator, compounds described in paragraphs 0175 to 0179 of WO 2021/020359 and compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used; The contents are incorporated herein.

As the photoradical polymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time. . Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of Japanese Patent Publication No. 2017-523465, Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, and photoinitiators (A) described in Japanese Patent No. 6469669. Oxime ester photoinitiators and the like, the contents of which are incorporated herein.

When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.5% by mass based on the total solid content of the resin composition. It is more preferably from 1.0 to 10% by weight, and even more preferably from 1.0 to 10% by weight. The photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range.
Note that since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating with an oven, a hot plate, or the like.

[Sensitizer]
The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and becomes electronically excited. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.
Usable sensitizers include benzophenone series, Michler's ketone series, coumarin series, pyrazole azo series, anilinoazo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, and pyrazolotriazole azo series. , pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, penzopyran type, indigo type and the like can be used.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso Naphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin Coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Also, other sensitizing dyes may be used.
For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. More preferably 0.5 to 10% by mass. The sensitizers 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 Polymer Dictionary, 3rd edition (edited by the Society of Polymer Science and Technology, 2005), pages 683-684. Examples of chain transfer agents include compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and RAFT (Reversible Addition Fragmentation chain Transfer). ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used in polymerization are used. These can generate radicals by donating hydrogen to low-activity radicals, or can generate radicals by being oxidized and then deprotonated. In particular, thiol compounds can be preferably used.

Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, the contents of which are incorporated herein.

When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the resin composition. More preferably, 0.5 to 5 parts by mass is even more preferred. The number of chain transfer agents may be one, or two or more. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.

<Base generator>
The resin composition of the present invention may also contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, and the cured product has good mechanical properties and chemical resistance. The performance as an interlayer insulating film for wiring layers is improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator is not particularly limited, and any known base generator can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.
Specific examples of nonionic base generators include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022/145355. The above description is incorporated herein.

Examples of the base generator include, but are not limited to, the following compounds.

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

Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of ammonium salts include, but are not limited to, the following compounds.

Specific examples of iminium salts include, but are not limited to, the following compounds.

When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
One type or two or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

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

Examples of esters 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, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate) , methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkyloxypropionate esters (e.g., methyl 2-alkyloxypropionate, 2-alkyloxypropionate) ethyl, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), Methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred. It is mentioned as something.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

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

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

Suitable examples of sulfoxides include dimethyl sulfoxide.

Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Preferred examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Alcohols include 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, Examples include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol One type of solvent selected from methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more types is preferable. Combination of dimethyl sulfoxide and γ-butyrolactone, combination of dimethyl sulfoxide and γ-valerolactone, combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropion Particularly preferred is the combination of amide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate. Further, it is also a preferred embodiment of the present invention that toluene is further added to the solvent used in combination in an amount of about 1 to 10% by mass based on the total mass of the solvent.
In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as a solvent is also one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone based on the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. preferable. Further, the upper limit of the content is not particularly limited and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as the specific resin contained in the resin composition.
Further, when dimethyl sulfoxide and γ-valerolactone are used together, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, based on the total mass of the solvent. It is more preferable to contain ~90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and more preferably to contain 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide. More preferred.

From the viewpoint of coating properties, the content of the solvent is preferably such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content may be adjusted depending on the desired thickness of the coating and the application method. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum adhesion aids, titanium adhesion aids, compounds having a sulfonamide structure and thiourea structure, phosphoric acid derivative compounds, and β-keto esters. compounds, amino compounds, etc.

〔Silane coupling agent〕
Examples of the silane coupling agent include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are not included herein. Incorporated. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group. Further, the following R includes a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and includes alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like. For example, from the viewpoint of desiring a desorption temperature of 160 to 180°C, caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
Moreover, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
Examples of such oligomer type compounds include compounds containing a repeating unit represented by the following formula (S-1).

In formula (S-1), R ^S1 represents a monovalent organic group, R ^S2 represents a hydrogen atom, a hydroxy group, or an alkoxy group, and n represents an integer of 0 to 2.
R ^S1 preferably has a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group. , (meth)acryloyloxy group, etc., preferably vinylphenyl group, (meth)acrylamide group or (meth)acryloyloxy group, more preferably vinylphenyl group or (meth)acryloyloxy group, (meth)acryloyloxy group, etc. More preferred are groups.
R ^S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
n represents an integer from 0 to 2, preferably 1.
Here, the structures of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound may be the same.
Here, it is preferable that n is 1 or 2 in at least one of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, and n is 1 or 2 in at least two. More preferably, n is 2, and even more preferably n is 1 in at least two cases.
Commercially available products can be used as such oligomer type compounds, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Aluminum-based adhesion aid]
Examples of the aluminum adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP2014-186186A and sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used. , the contents of which are incorporated herein.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin. By setting it above the above-mentioned lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it below the above-mentioned upper limit, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion improver, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Migration inhibitor>
It is preferable that the resin composition of the present invention further contains an aromatic heterocyclic compound different from the compound A described above. Such compounds include migration inhibitors.
It is preferable that the resin composition of the present invention further contains a migration inhibitor. By including a migration inhibitor, for example, when a resin composition is applied to a metal layer (or metal wiring) to form a film, metal ions derived from the metal layer (or metal wiring) may migrate into the film. can be effectively suppressed.
However, the compound corresponding to the above-mentioned compound A does not correspond to a migration inhibitor.

Migration inhibitors are not particularly limited, but include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring) , pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol type compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.

As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

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

Specific examples of migration inhibitors include the following compounds.

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

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

<Polymerization inhibitor>
It is preferable that the resin composition of the present invention contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

Specific compounds of the polymerization inhibitor include the compound described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Examples include oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like. This content is incorporated herein.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and 0.02 to 20% by mass based on the total solid content of the resin composition. It is more preferably 15% by mass, and even more preferably 0.05 to 10% by mass.

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

<Light absorber>
It is also preferable that the resin composition of the present invention contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

Whether or not a certain compound a contained in the resin composition corresponds to a light absorber (that is, whether the absorbance of the compound a at the exposure wavelength decreases upon exposure) can be determined by the following method.
First, a solution of compound a with the same concentration as that contained in the resin composition is prepared, and the molar extinction coefficient (mol ⁻¹ ·L·cm ⁻¹ , also referred to as “molar extinction coefficient 1”) of compound a at the wavelength of exposure light is determined. ). The above measurement is performed quickly so as to minimize the influence of changes such as a decrease in the molar extinction coefficient of compound a. As the solvent in the above solution, when the resin composition contains a solvent, that solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.
Next, the solution of compound a is irradiated with exposure light. The exposure amount is 500 mJ as an integrated amount for 1 mol of compound a.
Thereafter, using the solution of compound a after exposure, the molar extinction coefficient (mol ⁻¹ ·L·cm ⁻¹ , also referred to as “molar extinction coefficient 2”) of compound a at the wavelength of the exposure light is measured.
Calculate the attenuation rate (%) from the above molar extinction coefficient 1 and molar extinction coefficient 2 based on the following formula, and if the attenuation rate (%) is 5% or more, compound a has an absorbance at the exposure wavelength due to exposure. is determined to be a compound (that is, a light absorber) that reduces the
Attenuation rate (%) = 1 - molar extinction coefficient 2 / molar extinction coefficient 1 x 100
The attenuation rate is preferably 10% or more, more preferably 20% or more. Moreover, the lower limit of the above-mentioned attenuation rate is not particularly limited, and may be 0% or more.
When the resin composition is used to form a photosensitive film, the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed.
Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive. A photopolymerization initiator having sensitivity to a certain wavelength means that a polymerization initiation species is generated when the photopolymerization initiator is exposed to light at a certain wavelength.
In relation to the light source, the wavelength of the exposure light is (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength 436nm), H-line (wavelength 405nm), I-line (wavelength 365nm), Broad (3 wavelengths of g, h, i-line), (4) Excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer Laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) Extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) Electron beam, (7) YAG laser second harmonic 532 nm, third harmonic Examples include 355 nm.
The wavelength of the exposure light may be selected, for example, from a wavelength to which the photopolymerization initiator is sensitive, preferably the h-line (wavelength: 405 nm) or the i-line (wavelength: 365 nm), and more preferably the i-line (wavelength: 365 nm).

The light absorber may be a compound that generates radical polymerization initiation species upon exposure to light, but from the viewpoint of resolution and chemical resistance, it is preferably a compound that does not generate radical polymerization initiation species upon exposure.
Whether the light absorber is a compound that generates radical polymerization initiating species upon exposure to light is determined by the following method.
A solution containing a light absorber and a radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, the same compound as the radical crosslinking agent contained in the resin composition is used at the same concentration as the radical crosslinking agent in the solution. If the resin composition does not contain a radical crosslinker, methyl methacrylate is used at a concentration five times that of the light absorber.
After that, exposure light is irradiated. The exposure amount is 500 mJ as an integrated amount.
After exposure, the polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography, and if the ratio of the molar amount of the polymerizable compound to the total molar amount of the polymerizable compound is 10% or less, it is determined that the light absorber is It is determined that the compound does not generate radical polymerization initiation species upon exposure to light.
The molar amount ratio is preferably 5% or less, more preferably 3% or less. Further, the lower limit of the above molar amount ratio is not particularly limited, and may be 0%.
When the resin composition is used to form a photosensitive film, the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed.
Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive.

Examples of the compound that generates a radical polymerization initiator upon exposure to light include the same compounds as the above-mentioned photoradical polymerization initiators. When the composition contains a photoradical polymerization initiator as a light absorber, the one having the lowest ability to initiate polymerization of the generated radical species is the light absorber, and the others are the photopolymerization initiators.
Examples of compounds that do not generate radical polymerization initiation species upon exposure include photoacid generators, photobase generators, and dyes whose absorption wavelength changes upon exposure.
Among these, the light absorber is preferably a naphthoquinone diazide compound or a dye whose absorbance changes upon exposure, and more preferably a naphthoquinone diazide compound.
It is also conceivable to use a combination of a photoacid generator or a photobase generator and a compound whose absorbance at the exposure wavelength decreases depending on the pH, as the light absorber.

[Naphthoquinonediazide compound]
Examples of the naphthoquinonediazide compound include compounds that produce indenecarboxylic acid upon exposure and have a low absorbance at the exposure wavelength, and compounds having a 1,2-naphthoquinonediazide structure are preferred.
The naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonic acid ester of a hydroxy compound.
As the above-mentioned hydroxy compound, compounds represented by any of the following formulas (H1) to (H6) are preferred.

In formula (H1), R ¹ and R ² each independently represent a monovalent organic group, R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, and n1, n2, m1 and m2 are each independently an integer of 0 to 5, and at least one of m1 and m2 is an integer of 1 to 5.
In formula (H2), Z represents a tetravalent organic group, L ¹ , L ² , L ³ and L ⁴ each independently represent a single bond or a divalent organic group, and R ⁵ , R ⁶ , R ⁷ and ^R8 each independently represent a monovalent organic group, n3, n4, n5 and n6 each independently represent an integer of 0 to 3, m3, m4, m5 and m6 each independently represent 0 ˜2, and at least one of m3, m4, m5, and m6 is 1 or 2.
In formula (H3), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent organic group, L ⁵ each independently represents a divalent organic group, and n7 represents an integer from 3 to 8. represent.
In formula (H4), L ⁶ represents a divalent organic group, and L ⁷ and L ⁸ each independently represent a divalent organic group containing an aliphatic tertiary or quaternary carbon.
In formula (H5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a monovalent organic represents a group, L ⁹ , L ¹⁰ and L ¹¹ each independently represent a single bond or a divalent organic group, m7, m8, m9, m10 each independently represent an integer from 0 to 2, m7, At least one of m8, m9, and m10 is 1 or 2.
In formula (H6), R ⁴² , R ⁴³ , R ⁴⁴ , and R ⁴⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ⁴⁶ and R ⁴⁷ each independently represent a monovalent organic group. , n16 and n17 each independently represent an integer from 0 to 4, m11 and m12 each independently represent an integer from 0 to 4, and at least one of m11 and m12 is an integer from 1 to 4. be.

In formula (H1), R ¹ and R ² are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. . Examples of the monovalent organic group in R ¹ and R ² include a hydrocarbon group that may have a substituent, such as an aromatic hydrocarbon group that may have a substituent such as a hydroxy group. Can be mentioned.
In formula (H1), R ³ and R ⁴ are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. . Examples of the monovalent organic group in R ³ and R ⁴ include a hydrocarbon group that may have a substituent, such as a hydrocarbon group that may have a substituent such as a hydroxy group. .
In formula (H1), n1 and n2 are each independently preferably 0 or 1, and more preferably 0.
In formula (H1), m1 and m2 are preferably both 1.

The compound represented by formula (H1) is preferably a compound represented by any one of formulas (H1-1) to (H1-5).

In formula (H1-1), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen An atom or a group represented by the following formula (R-1) is more preferable.

In formula (R-1), R ²⁹ represents a hydrogen atom, an alkyl group, or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding site with another structure.
In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.

In formula (H1-2), R ²⁴ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15 and n16 each independently represent an integer from 0 to 2. R ³⁰ represents a hydrogen atom or an alkyl group.

In formula (H1-3), R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent a monovalent organic group, and are represented by a hydrogen atom, an alkyl group, or the above formula (R-1). It is preferable that it is a group.
In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, preferably 0 or 1.

The compound represented by formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).
The compound represented by the formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).
As the compound represented by formula (H1-3), compounds represented by the following formulas (H1-3-1) to (H1-3-3) are preferable.

In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulas (Z-1) to (Z-4). In the following formulas (Z-1) to (Z-4), * represents a bonding site with another structure.

In formula (H2), L ¹ , L ² , L ³ and L ⁴ are preferably each independently a single bond or a methylene group.
In formula (H2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently preferably an organic group having 1 to 30 carbon atoms.
In formula (H2), n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
In formula (H2), m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1.
Examples of the compound represented by formula (H2) include compounds having the following structure.

In formula (H3), R ⁹ and R ¹⁰ each independently preferably represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
In formula (H3), each L ⁵ is preferably independently a group represented by the following formula (L-1).

In formula (L-1), R ³⁰ represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding site with another structure.
In formula (H3), n7 is preferably an integer of 4 to 6.
Examples of the compound represented by formula (H3) include the following compounds. In the following formula, each n independently represents an integer of 0 to 9.

In formula (H4), L ⁶ is preferably -C(CF ₃ ) ₂ -, -S(=O) ₂ - or -C(=O)-.
In formula (H4), L ⁷ and L ⁸ are each independently preferably a divalent organic group having 2 to 20 carbon atoms.
Examples of the compound represented by formula (H4) include the following compounds.

In formula (H5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl , an alkoxy group, an allyl group or an acyl group.
In formula (H5), L ⁹ , L ¹⁰ and L ¹¹ each independently represent a single bond, -O-, -S-, -S(=O) ₂ -, -C(=O)-, -C( =O)O-, cyclopentylidene, cyclohexylidene, phenylene or a divalent organic group having 1 to 20 carbon atoms is preferred, and is represented by any of the following formulas (L-2) to (L-4). It is more preferable that it is a group.

In formulas (L-2) to (L-4), R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each independently represents a hydrogen atom or an alkyl group, n15 is an integer of 1 to 5, R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or an alkyl group, * Represents a binding site with other structures.
Examples of the compound represented by formula (H5) include the following compounds.

In formula (H6), R ⁴² , R ⁴³ , R ⁴⁴ , and R ⁴⁵ each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. , a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
In formula (H6), R ⁴⁶ and R ⁴⁷ are each independently preferably an alkyl group, an alkoxy group, or an aryl group, and more preferably an alkyl group.
In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
In formula (H6), n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3.
Examples of the compound represented by formula (H6) include the following compounds.

Other hydroxy compounds include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'- Methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3, 4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, 2,3 , 4,3',4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenones;
Polyhydroxyphenylalkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentyl ketone, 2,3,4-trihydroxyphenylhexyl ketone,
Bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl) Bis((poly)hydroxyphenyl) alkanes such as propane-1, nordihydroguaiaretic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane,
Polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate,
Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)-methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2 , 4,6-trihydroxybenzoyl)benzene or other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls,
Alkylene di(polyhydroxybenzoates) such as ethylene glycol di(3,5-dihydroxybenzoate) and ethylene glycol di(3,4,5-trihydroxybenzoate);
2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3',5'-biphenyltetrol, 2,4,2',4'-biphenyltetrol, 2,4, 6,3',5'-biphenylpentol, 2,4,6,2',4',6'-biphenylhexol, 2,3,4,2',3',4'-biphenylhexol, etc. polyhydroxybiphenyls,
Bis(polyhydroxy) sulfides such as 4,4'-thiobis(1,3-dihydroxy)benzene,
Bis(polyhydroxyphenyl) ethers such as 2,2',4,4'-tetrahydroxydiphenyl ether,
Bis(polyhydroxyphenyl) sulfoxides such as 2,2',4,4'-tetrahydroxydiphenyl sulfoxide,
Bis(polyhydroxyphenyl)sulfones such as 2,2',4,4'-diphenylsulfone,
Tris(4-hydroxyphenyl)methane, 4,4',4''-trihydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',3'',4''-tetrahydroxy- 3,5,3',5'-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4'-(3,4 -diol-benzylidene)bis[2,6-dimethylphenol], 4,4'-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4',2'',3 ″,4″-pentahydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 2,3,4,2′,3′,4′-hexahydroxy-5,5′-diacetyltriphenyl Methane, 2,3,4,2',3',4',3'',4''-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',6' -Polyhydroxytriphenylmethanes such as hexahydroxy-5,5'-dipropionyltriphenylmethane, 4,4'-(phenylmethylene)bisphenol, 4,4'-(1-phenyl-ethylidene)bis[2- methylphenol], polyhydroxytriphenylethanes such as 4,4′,4″-ethylidene-trisphenol,
3,3,3',3'-tetramethyl-1,1'-spirobi-indan-5,6,5',6'-tetrol, 3,3,3',3'-tetramethyl-1,1 '-Spirobi-indane-5,6,7,5',6',7'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobi-indane-4,5,6 ,4',5',6'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobi-indane-4,5,6,5',6',7'-hexol polyhydroxy spirobiindans such as, polyhydroxyflavans such as 2,4,4-trimethyl-2',4',7'-trihydroxyflavan,
3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3',4',5',6'-tetrahydroxyspiro[phthalide -3,9'-xanthene], flavonoid pigments such as morin, quercetin, rutin,
α, α′, α″-tris(4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α′, α″-tris(3,5-dimethyl-4-hydroxyphenyl) 1,3, 5-triisopropylbenzene, α,α′,α″-tris(3,5-diethyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α′,α″-tris(3,5 -di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α′,α″-tris(3,5-diisopropyl-4-hydroxyphenyl)1,3,5-triisopropyl Benzene, α,α′,α″-tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α′,α″-tris(3-methyl- 4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α′,α″-tris(3-methoxy-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α′,α ″-tris(2,4-dihydroxyphenyl)1,3,5-triisopropylbenzene, 1,3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris( 5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxyphenylthiomethyl)mesitylene, 1-[α-methyl-α-(4′-hydroxyphenyl) ethyl]-4-[α,α'-bis(4″-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4′-hydroxyphenyl)ethyl]-3-[α,α’-bis(4 ″-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3′,5′-dimethyl-4′-hydroxyphenyl)ethyl]-4-[α,α′-bis(3″,5 ″-dimethyl-4″-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3′-methyl-4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(3″-methyl -4″-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3′-methoxy-4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(3″-methoxy -4″-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2′,4′-dihydroxyphenyl)ethyl]-4-[α′,α′-bis(4″-hydroxyphenyl) ethyl]benzene, 1-[α-methyl(2′,4′-dihydroxyphenyl)ethyl]-3-[α′,α′-bis(4″-hydroxyphenyl)ethyl]benzene, etc. JP-A-4-253058 Polyhydroxy compounds described in JP-A-5-224410, such as α, α, α′, α′, α″, α″-hexakis-(4-hydroxyphenyl)-1,3,5-triethylbenzene, etc. JP-A-5-303200, EP-530148 of polyhydroxy compounds, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane, etc. poly(hydroxyphenyl)alkanes described in
p-bis(2,3,4-trihydroxybenzoyl)benzene, p-bis(2,4,6-trihydroxybenzoyl)benzene, m-bis(2,3,4-trihydroxybenzoyl)benzene, m- Bis(2,4,6-trihydroxybenzoyl)benzene, p-bis(2,5-dihydroxy-3-brombenzoyl)benzene, p-bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene , p-bis(2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-bis(2,3,4-trihydroxy-5-nitrobenzoyl)benzene, p-bis(2,3,4 -trihydroxy-5-cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzoyl)benzene, 1, 2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-tetrakis(2, 3,4-trihydroxybenzoyl)benzene, α,α'-bis(2,3,4-trihydroxybenzoyl)p-xylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl) ) mesilene,
2,6-bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis-(2-hydroxy-5'-methylbenzyl)-p-cresol, 2,6-bis -(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis(2,3,4 -trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-bis-(4-hydroxy-3,5-dimethylbenzyl)-pyrogallol, 2,6-bis-(4-hydroxy-3,5- dimethylbenzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethyl-phenol, 4,6-bis-(2, 3,4-trihydroxybenzyl)-2,5-dimethyl-phenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol , 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis(4 -Hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2',6,6'-tetrakis [( 4-hydroxyphenyl)methyl]-4,4'-methylene diphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylene Diphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3-methylphenyl)methyl]-4,4'-methylenediphenol, 2,2'-bis[(4-hydroxy-3 ,5-dimethylphenyl)methyl]6,6'-dimethyl-4,4'-methylenediphenol,2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1 , 1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol, bis(4-hydroxy-3,5-dimethylphenyl)-(4-hydroxy-3-methoxyphenyl) ) Methane, etc.
Furthermore, low-nuclear substances of phenolic resins such as novolac resins can also be used.

Examples of the naphthoquinone diazide sulfonic acid include 6-diazo 5,6-dihydro-5-oxo-1-naphthalene sulfonic acid, 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and mixtures thereof. It may also be used as

The method for producing naphthoquinone diazide sulfonyl ester of a hydroxy compound is not particularly limited, but for example, naphthoquinone diazide sulfonic acid is converted into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and the resulting naphthoquinone diazide sulfonyl chloride is condensed with a hydroxy compound. Obtained by reaction.
For example, esterification is performed by reacting a predetermined amount of a hydroxy compound and naphthoquinonediazide sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and the resulting product is washed with water. , can be obtained by drying.

The esterification rate of the naphthoquinonediazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, more preferably 20% or more. Further, the upper limit of the esterification rate is not particularly limited, and may be 100%.
The esterification rate can be confirmed by ¹ H-NMR or the like as the proportion of esterified groups among the hydroxy groups of the hydroxy compound.

In addition, compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A can also be used as light absorbers.

<Other additives>
The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, etc., as long as the effects of the present invention can be obtained. Contains organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g. antifoaming agents, flame retardants, etc.). You can stay there. In addition, the resin composition of the present invention may also contain a urea compound, a carbodiimide compound, or an isourea compound. By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. When blending these additives, their total content is preferably 3% by mass or less based on the solid content of the resin composition of the present invention.

Examples of these other additives include compounds described in paragraphs 0316 to 00358 of International Publication No. 2022/145355. The above description is incorporated herein.

<Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm ² /s to 12,000 mm ² /s, more preferably 2,000 mm ² /s to 10,000 mm ² /s, and 2,500 mm ² /s to 8,000 mm. ² /s is more preferable. Within the above range, it becomes easy to obtain a coating film with high uniformity. If it is 1,000 mm ² /s or more, it is easy to coat the film with the thickness required for, for example, an insulating film for rewiring, and if it is 12,000 mm ² /s or less, the coating surface quality is excellent. A coating film is obtained.

<Restrictions on substances contained in the resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will improve.
Methods for maintaining the moisture content include adjusting the humidity during storage conditions and reducing the porosity of the storage container during storage.

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, from the viewpoint of insulation. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals included as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.

Further, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a method for reducing metal impurities that is unintentionally included in the resin composition of the present invention is to select a raw material with a low metal content as a raw material constituting the resin composition of the present invention. Methods include filtering the raw materials constituting the product, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.

Considering the use as a semiconductor material, the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. is even more preferable. Among these, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

As a container for storing the resin composition of the present invention, a conventionally known container can be used. For the purpose of suppressing the contamination of impurities into raw materials and the resin composition of the present invention, the storage container may be a multilayer bottle whose inner wall is made of 6 types of 6 layers of resin, or a container with 7 layers of 6 types of resin. It is also preferred to use structured bottles. Examples of such a container include the container described in JP-A No. 2015-123351.

<Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing a resin composition.
The resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the purpose, such as film, rod, sphere, or pellet form. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, we can select the shape of the cured product depending on the application, such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting heat dissipation function. You can also. The thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

<Characteristics of cured product of resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be performed by a conventionally known method.
Examples of the mixing method include mixing using a stirring blade, mixing using a ball mill, and mixing using a rotating tank.
The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

In order to remove foreign substances such as dust and fine particles from the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). The filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination. Examples of the connection mode include a mode in which an HDPE filter with a pore diameter of 1 μm is connected in series as the first stage and an HDPE filter with a pore diameter of 0.2 μm as the second stage. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure. When performing filtration under pressure, the pressure to be applied is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, for example. Even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and degassed.

(Method for producing cured product)
The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.
The method for producing a cured product includes the above film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposure step using a developer to form a pattern. It is more preferable to include a developing step.
The method for producing a cured product includes the film formation step, the exposure step, the development step, a heating step of heating the pattern obtained in the development step, and a post-development exposure step of exposing the pattern obtained in the development step. It is particularly preferable to include at least one of them.
Moreover, it is also preferable that the method for producing a cured product includes the film forming step and the step of heating the film.
The details of each step will be explained below.

<Film formation process>
The resin composition of the present invention can be used in a film forming step in which a film is formed by applying it on a substrate.
The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.

〔Base material〕
The type of base material can be appropriately determined depending on the purpose and is not particularly limited. Examples of the base material include semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, magnetic films, reflective films, Ni, Cu, A metal base material such as Cr or Fe (for example, a base material formed from a metal, or a base material on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Examples include glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDP). The base material is particularly preferably a semiconductor production base material, and more preferably a silicon base material, a Cu base material, and a mold base material.
These base materials may be provided with a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like on the surface.
The shape of the base material is not particularly limited, and may be circular or rectangular.
As for the size of the base material, if it is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm. If it is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.
As the base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) is used.

When forming a film by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or metal layer serves as the base material.

Coating is preferred as a means for applying the resin composition onto the substrate.
Specifically, the methods to be applied include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, Examples include inkjet method. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is preferable, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and slit coating method are preferable. A coating method is more preferred. A film with a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition depending on the means to be applied. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and for circular substrates such as wafers, spin coating, spray coating, inkjet methods, etc. are preferable, and for rectangular substrates, slit coating, spray coating, etc. method, inkjet method, etc. are preferred. In the case of spin coating, it can be applied, for example, at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
A pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.

<Drying process>
After the film forming step (layer forming step), the film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably performed after the film forming step and before the exposure step.
The drying temperature of the membrane in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Alternatively, drying may be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure process>
The film may be subjected to an exposure process that selectively exposes the film.
The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step.
Selectively exposing means exposing a portion of the film. Furthermore, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed in the film.
The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is preferably 50 to 10,000 mJ/cm ² and more preferably 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm. preferable.

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

In relation to the light source, the exposure wavelength is: (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength: 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (three wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), _F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. Can be mentioned. For the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferable, and exposure using i-line is more preferable from the viewpoint of exposure sensitivity.
The method of exposure is not particularly limited, and may be any method as long as at least a portion of the film made of the resin composition of the present invention is exposed to light, and examples thereof include exposure using a photomask, exposure using a laser direct imaging method, etc. .

<Post-exposure heating process>
The film may be subjected to a heating step after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
The post-exposure heating step can be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min, from the temperature at the start of heating to the maximum heating temperature.
Further, the temperature increase rate may be changed as appropriate during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used.
It is also preferable that the heating be performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.

<Developing process>
The exposed film may be subjected to a development step of developing a pattern using a developer.
That is, the method for producing a cured product of the present invention may include a development step of developing the film exposed in the exposure step using a developer to form a pattern.
By performing development, one of the exposed and non-exposed areas of the film is removed and a pattern is formed.
Here, development in which the non-exposed portions of the film are removed in the developing step is referred to as negative development, and development in which the exposed portions of the film are removed in the development step is referred to as positive development.

[Developer]
Examples of the developer used in the development step include an alkaline aqueous solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. , TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole , piperidine is preferred, and TMAH is more preferred. The content of the basic compound in the developer is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and even more preferably 0.3 to 3% by weight based on the total weight of the developer.

When the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent. This content is incorporated herein. In addition, alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc.Amides include N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.

When the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In the present invention, a developer containing at least one member selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred. A developer containing at least one selected from the group consisting of and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 90% by mass or more. Moreover, the said content may be 100 mass %.

When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, performance such as elongation at break of the pattern may be improved.

As the basic compound, an organic base is preferable from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).
As the basic compound, a basic compound having an amino group is preferable, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferable, but in order to promote the imidization reaction, A primary amine, a secondary amine, a tertiary amine or an ammonium salt is preferred, a secondary amine, a tertiary amine or an ammonium salt is more preferred, a secondary amine or a tertiary amine is even more preferred, and a tertiary amine is particularly preferred.
From the viewpoint of the mechanical properties (elongation at break) of the cured product, the basic compound is preferably one that does not easily remain in the cured film (obtained cured product), and from the viewpoint of promoting cyclization, it It is preferable that the residual amount is not likely to decrease before heating.
Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
The boiling point of the basic compound is preferably higher than the boiling point of the organic solvent contained in the developer minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer.
For example, when the organic solvent has a boiling point of 100°C, the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.
The developer may contain only one type of basic compound, or may contain two or more types of basic compounds.

Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N , N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine , N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, Tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N, Examples include N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, and the like.

The preferred embodiments of the base generator are the same as the preferred embodiments of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and 5% by mass or less based on the total mass of the developer. More preferred. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.
If the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the developer. is also preferable.
The developer may contain only one type of at least one of a basic compound and a base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.

The developer may further contain other components.
Examples of other components include known surfactants and known antifoaming agents.

[Developer supply method]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and methods include immersing the base material on which the film is formed in the developer, and supplying the developer to the film formed on the base material using a nozzle. There is a method of paddle development, or a method of continuously supplying a developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
From the viewpoint of permeability of the developer, removability of non-image areas, and production efficiency, it is preferable to supply the developer using a straight nozzle or continuously using a spray nozzle. From the viewpoint of permeability, a method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer using a straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, the base material is spun, and the developer is applied to the base material. A process of removing from above may be adopted, or this process may be repeated multiple times.
Methods for supplying the developer in the development process include a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is applied to the base material using ultrasonic waves. Examples include a step of vibrating with the like, and a step of combining these.

The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

In the development step, after the treatment using the developer, the pattern may be further cleaned (rinsed) with a rinse solution. Alternatively, a method such as supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted.

[Rinse liquid]
When the developing solution is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) is used as the rinsing solution. be able to.

Examples of the organic solvent when the rinsing liquid contains an organic solvent include the same organic solvents as those exemplified in the case where the above-mentioned developer contains an organic solvent.
The organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent in which the pattern has a lower solubility than the organic solvent contained in the developer.

When the rinsing liquid contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and cyclohexanone or PGMEA. More preferred.

When the rinsing liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinsing liquid. Moreover, the organic solvent may be 100% by mass with respect to the total mass of the rinsing liquid.

The rinsing liquid may contain at least one of a basic compound and a base generator.
Although not particularly limited, when the developer contains an organic solvent, one preferred embodiment of the present invention is an embodiment in which the rinsing solution contains the organic solvent and at least one of a basic compound and a base generator.
Examples of the basic compound and base generator contained in the rinsing solution include the compounds exemplified as the basic compound and base generator that may be included when the above-mentioned developer contains an organic solvent, and preferred embodiments also include. The same is true.
The basic compound and base generator contained in the rinsing liquid may be selected in consideration of the solubility in the solvent in the rinsing liquid.

When the rinsing liquid contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinsing liquid. preferable. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.
If the basic compound or base generator is solid in the environment where the rinse solution is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the rinse solution. is also preferable.
When the rinsing liquid contains at least one of a basic compound and a base generator, the rinsing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. . When at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.

The rinse solution may further contain other components.
Examples of other components include known surfactants and known antifoaming agents.

[How to supply rinsing liquid]
There are no particular restrictions on the method of supplying the rinsing liquid as long as the desired pattern can be formed, such as immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by piling up the liquid, or supplying the rinsing liquid to the substrate by showering. There is a method of continuously supplying the rinsing liquid onto the substrate using a means such as a straight nozzle.
From the viewpoint of permeability of the rinsing liquid, removability of non-image areas, and production efficiency, there are methods of supplying the rinsing liquid using a shower nozzle, straight nozzle, spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of permeability of the rinsing liquid into the image area, a method of supplying the rinsing liquid using a spray nozzle is more preferable. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
That is, the rinsing step is preferably a step in which the rinsing liquid is supplied to the exposed film through a straight nozzle or continuously, and more preferably a step in which the rinsing liquid is supplied through a spray nozzle.
Methods for supplying the rinsing liquid in the rinsing process include a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept in a substantially stationary state on the substrate, and a process in which the rinsing liquid is applied to the substrate using ultrasonic waves. It is possible to adopt a process of vibrating the wafer, etc., and a process of combining these.

The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

The developing step may include a step of bringing the processing solution into contact with the pattern after processing using the developer or after cleaning the pattern with a rinse solution. Alternatively, a method may be adopted in which the processing liquid is supplied before the developing liquid or the rinsing liquid in contact with the pattern is completely dried.

Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
Preferred embodiments of the organic solvent and at least one of the basic compound and base generator are the same as the preferred embodiments of the organic solvent and at least one of the basic compound and base generator used in the above-mentioned rinsing liquid. .
The method for supplying the treatment liquid to the pattern can be the same as the method for supplying the rinsing liquid described above, and the preferred embodiments are also the same.

The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example.
In addition, if the basic compound or base generator is solid in the environment where the treatment liquid is used, the content of the basic compound or base generator is 70 to 100% by mass based on the total solid content of the treatment liquid. It's also good to have one.
When the processing liquid contains at least one of a basic compound and a base generator, the processing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. . When at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.

<Heating process>
The pattern obtained by the development step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step.
Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film forming step.
In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as polyimide.
Further, crosslinking of unreacted crosslinkable groups in the specific resin or a crosslinking agent other than the specific resin also progresses.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and the action of a base generated from the base generator.

Heating in the heating step is preferably carried out at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is 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, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C/min or less, curing can be achieved. Residual stress in objects can be alleviated.
In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8°C/second, more preferably 2 to 7°C/second, and 3 to 6°C. C/sec is more preferred.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30°C higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a lower temperature by ~200°C.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. .
The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating may be performed in stages. As an example, the temperature is raised from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, and the temperature is raised from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. , etc. may be performed. It is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment step may be performed in two or more steps, for example, the first pretreatment step is performed at a temperature of 100 to 150°C, and then the second pretreatment step is performed at a temperature of 150 to 200°C. Good too.
Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5° C./min.

The heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and includes, for example, a hot plate, an infrared oven, an electric oven, a hot air oven, an infrared oven, and the like.

<Post-development exposure process>
The pattern obtained in the development process (in the case of performing a rinsing process, the pattern after rinsing) is subjected to a post-development exposure process in which the pattern after the development process is exposed to light, instead of or in addition to the above heating process. may be served.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor, etc. progresses due to the exposure of a photobase generator, a reaction in which the elimination of an acid-decomposable group progresses due to exposure to a photoacid generator, etc. are promoted. can do.
In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
The post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, and it is preferable to use broadband light.

<Metal layer formation process>
The pattern obtained by the development process (preferably one that has been subjected to at least one of a heating process and a post-development exposure process) may be subjected to a metal layer forming process of forming a metal layer on the pattern.
That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step). It is preferable to include.

As the metal layer, existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879, JP 2001-521288, JP 2004-214501, JP 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 are used. can do. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof can be used. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned. A preferred embodiment of plating includes electrolytic plating using copper sulfate or copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm at the thickest part.

<Application>
Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For information on these uses, see, for example, Science & Technology Co., Ltd., "Advanced Functionality and Applied Technology of Polyimide," April 2008, Masaaki Kakimoto/Supervised, CMC Technical Library, "Basics and Development of Polyimide Materials," November 2011. You can refer to "Latest Polyimide Fundamentals and Applications" published by Japan Polyimide and Aromatic Polymer Research Group/editor, NTS, August 2010, etc.

The method for producing a cured product of the present invention or the cured product of the present invention can be used for producing plates such as offset plates or screen plates, for etching molded parts, and for use in protective lacquers and dielectric layers in electronics, particularly microelectronics. It can also be used for manufacturing.

(Laminated body and method for manufacturing the laminate)
The laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminate is a laminate including two or more layers made of cured material, and may be a laminate in which three or more layers are laminated.
At least one of the two or more layers made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and shrinkage of the cured product or deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the above-mentioned laminate are layers made of the cured product of the present invention.

That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured product and includes a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product during the method for producing the cured product which is performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layered structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order, is preferred. It will be done.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer consisting of the first cured product and the resin composition of the present invention used for forming the layer consisting of the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Lamination process>
It is preferable that the method for manufacturing a laminate of the present invention includes a lamination step.
The lamination process refers to (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and development on the surface of the pattern (resin layer) or metal layer again. This is a series of steps including performing at least one of the post-exposure steps in this order. However, an embodiment may be adopted in which at least one of (a) the film forming step and (d) the heating step and the post-development exposure step are repeated. Furthermore, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. It goes without saying that the lamination step may further include the above-mentioned drying step and the like as appropriate.

If a lamination step is further performed after the lamination step, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.

The above lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a configuration in which the number of resin layers is 2 or more and 20 or less, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferable, and a configuration in which the number of resin layers is 2 or more and 9 or less is more preferable. .
Each of the above layers may have the same composition, shape, thickness, etc., or may have different compositions, shapes, thicknesses, etc.

In the present invention, it is particularly preferable that after providing the metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, the following steps are repeated in the following order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of the heating step and post-development exposure step, and (e) metal layer formation step. Alternatively, an embodiment may be mentioned in which (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated. can.

(Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to the surface activation treatment. After performing this step, the metal layer forming step may be performed.
The surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the resin composition layer after exposure. Both may be performed at least in part, respectively. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on part or all of the region of the metal layer on which the resin composition layer is to be formed. By performing surface activation treatment on the surface of the metal layer in this way, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface.
It is preferable that the surface activation treatment is also performed on part or all of the resin composition layer (resin layer) after exposure. By performing surface activation treatment on the surface of the resin composition layer in this way, it is possible to improve the adhesion with the metal layer or resin layer provided on the surface that has been surface activated. In particular, when the resin composition layer is hardened, such as when performing negative development, it is less likely to be damaged by surface treatment and adhesion is likely to be improved.
The surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated herein.

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device containing the cured product or laminate of the present invention.
The present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate.
As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 of JP 2016-027357A and the description in FIG. 1 can be referred to, Their contents are incorporated herein.

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

<Method for producing cyclized resin precursor>
[Synthesis Example 1: Synthesis of cyclized resin precursor (resin 1)]
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, and 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136 g of tetrahydrofuran were added. 83 g of pyridine was added thereto and stirred at room temperature (25° C.), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring, followed by addition of 4,4'-diaminodiphenyl ether (DADPE). A suspension of 27.42 g in 119.73 g of tetrahydrofuran was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and vacuum dried to obtain 80.3 g of powdered Resin 1. When the molecular weight of Resin 1 was measured by gel permeation chromatography (standard polystyrene standard), the weight average molecular weight (Mw) was 20,000. It was confirmed by ¹ H-NMR that the structure of Resin 1 was represented by the following formula (P-1).
In addition, the molar amount of carboxyester whose alcohol-derived structure is a 2-hydroxyethyl methacrylate-derived structure (i.e., methacryloxyethyloxycarbonyl group) relative to the total molar amount of all carboxy groups and carboxyesters contained in resin 1. was 95.6 mol%, and the molar amount of carboxyester whose alcohol-derived structure is an ethyl alcohol-derived structure (that is, ethoxycarbonyl group) was 4.2 mol%.

[Synthesis Example 2: Synthesis of cyclized resin precursor (resin 2)]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and heated at 60°C. The mixture was stirred at the same temperature for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C and 17.0g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10 ± 5 °C. and the mixture was stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added and stirred at room temperature for 1 hour.
Then, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered again and dried at 45° C. for 3 days under reduced pressure.
After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Thereafter, 3000 g of ethanol was added and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto, and the mixture was stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45° C. for 24 hours to obtain 45.1 g of Resin 2.
It was confirmed by ¹ H-NMR that the structure of Resin 2 was a structure represented by the following formula (P-2). When the molecular weight of Resin 2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, resin 2 with an Mw of 5,000, resin 2 with an Mw of 10,000, and resin 2 with an Mw of 30,000 can also be used. Synthesized.
Also, the molar amount of carboxyester whose alcohol-derived structure is a 2-hydroxyethyl methacrylate-derived structure (i.e., methacryloxyethyloxycarbonyl group) relative to the total molar amount of all the carboxy groups and carboxyesters contained in the resin 2. was 94.5 mol%, and the molar amount of carboxyester whose alcohol-derived structure is an ethyl alcohol-derived structure (that is, ethoxycarbonyl group) was 4.0 mol%.

[Synthesis Examples 3 to 9: Synthesis of cyclized resin precursors (Resin 3 to Resin 9)]
Resins 3 to 9 having structures represented by any of the following formulas (P-3) to (P-9) were synthesized in the same manner as in Synthesis Example 2, except that the compounds used were changed as appropriate.
Mw of Resin 3 is 20,000, Mw of Resin 4 is 20,000, Mw of Resin 5 is 20,000, Mw of Resin 6 is 20,000, Mw of Resin 7 is 20,000, Mw of Resin 8 is 20,000, and the Mw of Resin 9 was 20,000.

[Synthesis Example 10: Synthesis of cyclized resin precursor (resin 10)]
In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while removing water. was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (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, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. ) was added and diluted.
The reaction solution was precipitated in 1 liter of methanol and stirred for 15 minutes at a speed of 3000 rpm. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40° C. for one day under reduced pressure to obtain Resin 10. When the molecular weight of Resin 10 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. ¹ H-NMR confirmed that the structure of resin 10 was a structure represented by the following formula (P-10).

[Synthesis Example 11: Synthesis of cyclized resin precursor (resin 11)]
Resin 11 having a structure represented by the following formula (P-11) was synthesized in the same manner as in Synthesis Example 10, except that the compounds used were changed as appropriate.
The Mw of Resin 11 was 20,000.

<Examples and comparative examples>
In each Example, the components listed in the table below were mixed to obtain each resin composition. Further, in a comparative example, the components listed in the table below were mixed to obtain a comparative composition.
Specifically, the content (compounding amount) of each component listed in the table other than the solvent was the amount (parts by mass) listed in the "parts by mass" column in each column of the table.
The content (compounding amount) of the solvent is determined so that the solid content concentration of the composition is the value (mass %) of "solid content concentration" in the table, and the ratio of the content of each solvent to the total mass of the solvent (mass %) is determined. The ratio) was set to be the ratio described in the "Ratio" column in the table.
The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm.
Furthermore, in the table, the description "-" indicates that the composition does not contain the corresponding component.

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

〔resin〕
・Resin 1 to Resin 11: Resin 1 to Resin 11 obtained by the above synthesis example

[Monomer (polymerizable compound)]
-M-1: Compound with the following structure. The subscript in parentheses indicates the number of repetitions.

・DPHA: dipentaerythritol hexaacrylate

[Polymerization initiator or photoacid generator]
・I-1 to I-5: Compounds with the following structure ・I-6: Omnirad 1312 (manufactured by IGM)
・I-7: Omnirad TPO H (manufactured by IGM)

[Base generator]
・A-1 to A-5: Compounds with the following structure

[Polymerization inhibitor]
・B-1 to B-4: Compounds with the following structure

[Silane coupling agent (metal adhesion improver)]
- C-1 to C-3: Compounds with the following structure. In the following formula, Et represents an ethyl group.
・C-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent with protected isocyanate group)
・C-5: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent that is an acrylic group-containing oligomer)

[Migration inhibitor]
・D-1 to D-4: Compounds with the following structure

〔Additive〕
- E-1 to E-7, E-9: Compounds with the following structure E-8 was synthesized by the method described in paragraph 0184 of JP 2019-206689 A.
Specifically, 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Honshu) was prepared in a separable flask equipped with a stirrer, dropping funnel, and thermometer. 30 g (0.0707 mol) of Tris-PA (trade name, manufactured by Kagaku Kogyo Co., Ltd.) was mixed with 47.49 g (0.07 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride in an amount corresponding to 83.3 mol% of the OH group. After stirring and dissolving .177 mol) in 300 g of acetone, the flask was adjusted to 30°C in a constant temperature bath.
Next, 17.9 g of triethylamine was dissolved in 18 g of acetone and charged into a dropping funnel, which was then dropped into the flask over 30 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes, and then hydrochloric acid was added dropwise and stirring was continued for an additional 30 minutes to complete the reaction. The reaction was then filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a beaker, and the filtrate was added dropwise to the mixture with stirring to obtain a precipitate. This precipitate was washed with water, filtered, and then dried at 40° C. under reduced pressure for 48 hours to obtain E-8.

[Compound A]
F-1 to F-20: Compounds with the following structure. F-1 to F-20 are compounds corresponding to the above-mentioned compound A.
FR-1: Compound with the following structure. FR-1 is a compound that does not fall under the above-mentioned compound A.

-Synthesis of F-2-
In a flask, 8.3 g of tert-butyl N-(2-aminoethyl)carbamate, 4.0 g of 6-chloropurine, 15.7 g of triethylamine, and 70 g of 1-butanol were mixed at room temperature, heated to 80 °C, and stirred for 3 hours. did. After cooling the reaction solution to room temperature, the solution and solid precipitate were separated by filtration. The filtered solid was suspended in 200 mL of water and stirred at room temperature for 1 hour, and then the solution and solid were separated by filtration. Further, the filtered solid was suspended in 200 mL of ethyl acetate, stirred at room temperature for 1 hour, and then the solution and solid were separated by filtration. The obtained solid was air-dried to obtain 5.64 g of target product F-2 (yield 78%).
1H-NMR, 400MHz, δ((DMSO-d6) ppm: 1.29 and 1.36 (9H, a pair of s), 3.17 (2H, q, J=6 Hz), 3.52 (2H, br-s), 6.49 and 6.92 (1H, a pair of s), 7.58 (1H, br-s), 8.10 (1H, s), 8.18 (1H, s), 12.73 (1H, br-s).
-Synthesis of F-4-

In a flask, 5.1 g of adenine, 19.4 g of di-tert-butyl dicarbonate, and 89 g of tetrahydrofuran were mixed at room temperature, and after adding 0.3 g of 4-dimethylaminopyridine, the mixture was stirred for 16 hours. The solvent of the reaction solution was distilled off under reduced pressure, and the obtained solid was dissolved in 80 mL of ethyl acetate. The organic layer was separated and washed in order with 40 mL of 1 M hydrochloric acid (once), 40 mL of water (twice), and 40 mL of diluted layered water (once), dried over sodium sulfate, and the filtrate was vacuumed. F-4-1 was obtained as a crude product by concentration below.
In a flask, 13.1 g of F-4-1, 180 mL of 1 M aqueous sodium hydroxide solution, and 375 mL of ethanol were mixed at room temperature and stirred for 72 hours. After cooling the reaction solution to 0° C., 120 mL of 1 M hydrochloric acid was added dropwise to neutralize the reaction solution (pH 7), and the mixture was stirred at room temperature for 5 hours. The reaction solution was extracted three times with 133 mL of dichloromethane, the organic layer was dried over sodium sulfate, and the filtrate was concentrated under reduced pressure to obtain a crude product. The obtained solid was suspended in 100 mL of water, stirred at room temperature for 1 hour, and then the solution and solid were separated by filtration. Furthermore, the solid collected by filtration was suspended in 20 mL of ethyl acetate, and after stirring at 60° C. for 1 hour, the solution and solid were separated by filtration. The obtained solid was air-dried to obtain 1.28 g of target product F-4 (yield 18%).
1H-NMR, 400MHz, δ((DMSO-d6) ppm: 1.52 (9H, s), 8.41 (1H, s), 8.56 (1H, s), 10.51 (1H, br-s), 12.23 (1H, br -s).
-Synthesis of F-20-

In a flask, 36.1 g of ethylenediamine, 9.3 g of 6-chloropurine, 30.0 g of water, and 146.0 g of 1-butanol were mixed at room temperature, heated to 80° C., and then stirred for 5 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated under heating and reduced pressure. The obtained solid was suspended in 200 mL of methanol, and after stirring at room temperature for 1 hour, the solution and solid were separated by filtration. Further, the solid collected by filtration was suspended in 200 mL of acetone, and after stirring at room temperature for 1 hour, the solution and solid were separated by filtration. By air-drying the obtained solid, 9.16 g of target product F-20-1 was obtained (yield: 86%).
1H-NMR, 400MHz, δ((D2O) ppm: 3.02 (2H, t, J=6 Hz), 3.57 (2H, t, J=6 Hz), 7.86 (1H, s), 7.91 (1H, d, J=1 Hz).
In a flask, 3.0 g of F-20-1, 4.6 g of 2-coumaranone, and 16.1 g of N,N-dimethylformamide were mixed at room temperature, heated to 80° C., and then stirred for 14 hours. After cooling the reaction solution to 0° C., 100 mL of diisopropyl ether was added and stirred for 30 minutes, and the precipitated solid was separated by filtration. The obtained solid was suspended in 100 mL of water, stirred at room temperature for 1 hour, and then the solution and solid were separated by filtration. Further, the filtered solid was suspended in 70 mL of acetone, stirred at 50° C. for 1 hour, and then cooled to 0° C., and the solution and solid were separated by filtration. The obtained solid was air-dried to obtain 2.14 g of the target product F-20 (yield 41%).
1H-NMR, 400MHz, δ((DMSO-d6+D2O) ppm: 3.39 (2H, t, J=6 Hz), 3.40 (2H, s), 3.64 (2H, br-s), 6.71 (1H, td , J=7, 1 Hz), 6.79 (1H, d, J=8 Hz), 7.02 (1H, d, J=7 Hz), 7.08 (1H, td, J=8, 1 Hz), 8.13 (1H , s), 8.16 (1H, s).

〔solvent〕
・NMP: N-methyl-2-pyrrolidone ・EL: ethyl lactate ・DMSO: dimethyl sulfoxide ・GBL: γ-butyrolactone ・GVL: γ-valerolactone ・MDMPA: 3-methoxy-N,N-dimethylpropanamide ・Toluen: toluene

<Evaluation>
[Evaluation of adhesion after heat resistance test]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied in a layered manner onto a copper substrate by a spin coating method to form a resin composition layer or a comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, and the film thickness (μm) described in the column of the table was applied to the copper substrate. A resin composition layer or a comparative composition layer having a uniform thickness was used. The resin composition layer or the comparative composition layer on the copper substrate was exposed to an exposure energy of 500 mJ/ ^cm2 , and in the examples where "negative" was written in the "Development conditions" column of the table, a 100 μm square square shape was formed. In examples where "Positive" is written in the "Development Conditions" column of the table, a photomask with a non-mask area formed thereon is used, and a photomask with a 100 μm square mask area formed thereon is used. It was exposed to light having the exposure wavelength (nm) described in the "Exposure wavelength (nm)" column.
In the examples described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source.
In the example where "D" is written in the exposure condition column, a direct exposure device (Adtech DE-6UH III) is used as the light source, and a laser direct imaging exposure is performed on a 100 μm square area without using a photomask. went.
Thereafter, development was performed for 60 seconds using the developer shown in the table to obtain a square resin layer of 100 μm square. The description of "TMAH aqueous solution" in the table means a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
In examples where a numerical value is listed in the "cure temperature" column, the exposed resin composition layer is heated at a rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the "Cure Temperature (° C.)" column of the table, the temperature was maintained for the time "Cure Time (min)" in the table to obtain a cured product.
In the examples where "IR" is written in the "Cure temperature (℃)" column, the resin film obtained in each example was heated using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.). The temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained for the “cure time (min)” in the table to obtain a cured product.
The obtained copper substrate with the cured product was placed in a tank at a temperature of 175° C. in the atmosphere for 192 hours.
The shear force was measured on a 100 μm square cured product on a copper substrate using a bond tester (Condor Sigma, manufactured by XYZTEC) in an environment of 25 ° C. and 65% relative humidity (RH). , evaluated according to the following evaluation criteria. The evaluation results are listed in the column of "Adhesion after heat resistance test" in the table. It can be said that the greater the shearing force, the better the adhesion of the cured film after the heat resistance test.
-Evaluation criteria-
A: Shear force exceeded 30 gf.
B: Shear force exceeded 25 gf and was 30 gf or less.
C: Shear force exceeded 20 gf and was 25 gf or less.
D: Shear force was 20 gf or less.
Moreover, 1 gf is 0.00980665N.

[Composition stability]
The resin composition or comparative composition prepared in each Example or Comparative Example was allowed to stand at 38° C. for 3 days under light shielding conditions. After the above-mentioned standing is completed, the viscosity is measured using a viscometer (Toki Sangyo RE-85L), and compared with the initial state (before the above-mentioned standing), the viscosity change rate after the above-mentioned standing is completed is determined. It was calculated according to the following formula and evaluated according to the following evaluation criteria. The evaluation results are listed in the "composition stability" column of the table. It can be said that the smaller the viscosity change rate, the more excellent the composition stability is.
Viscosity change rate (%) = | (Viscosity after the completion of the above-mentioned standing − Viscosity before the above-mentioned standing) | / (Viscosity before the above-mentioned standing) × 100
-Evaluation criteria-
A: The absolute value of the above viscosity change rate was 3% or less.
B: The absolute value of the viscosity change rate was more than 3% and less than 5%.
C: The absolute value of the viscosity change rate was more than 5% and less than 8%.
D: The absolute value of the viscosity change rate was more than 8% and less than 10%.
E: The absolute value of the above viscosity change rate exceeded 10%.

From the above results, it can be seen that the cured product formed from the resin composition of the present invention has excellent adhesion even after the heat resistance test.
The comparative composition according to Comparative Example 1 does not contain Compound A. It can be seen that such comparative compositions have poor adhesion after the heat resistance test.

<Example 101>
The resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100°C for 5 minutes to determine the film thickness. After forming a 20 μm photoresist film, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the above exposure, it was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layer had excellent insulation properties.
Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for a rewiring layer, it was confirmed that it operated without any problems.

Claims

At least one resin selected from the group consisting of cyclized resins and precursors thereof;
A resin composition comprising a compound A corresponding to at least one of the following compounds a1 and compound a2.
Compound a1: Protected primary amine structure, oxazole ring, thiazole ring, pyrimidine ring, Schiff base group, phenolic hydroxyl group, group represented by the following formula (1-1), the following formula (1-2) ) and a group represented by the following formula (1-4) Compound a2 having at least one structure selected from the group consisting of a group represented by the following formula (1-4): a protected primary alkylamine structure, and Having a group represented by any of the following formulas (1-1) to (1-4)

In formula (1-1), X 1 represents -C(R x ) 2 -, -NR x -, -S-, or -O- , and X 2 to =N-, and when X 1 is -C(R x ) 2 - or -O-, at least two of X 2 to X 7 represent =N-, and X 1 is -NR In the case of S-, at least one of X 2 to X 7 represents =N-, and each R and one of X 4 to X 7 contains R x which is a bonding site with another structure represented by *, and in the group represented by formula (1-1), There is only one R x that is a binding site with the structure.
In formula (1-2), X 14 represents -C(R x ) 2 -, -NR x -, -S-, or -O- , and X 8 to =N-, and when X 14 is -C(R x ) 2 - or -O-, at least two of X 8 to X 13 represent =N-, and X 14 is -NR When S-, at least one of X 8 to X 13 represents =N-, and each R X independently represents a bonding site with another structure represented by *, a hydrogen atom, or a monovalent substituent , one of X 8 , X 13 and X 14 contains R x which is a bonding site with another structure represented by *, and in the group represented by formula (1-2), There is only one R x that is a binding site with other structures.
In formula (1-3), X 15 represents -C(R x ) 2 -, -NR x -, -S-, or -O- , and X 16 to =N-, and when X 15 is -C(R x ) 2 - or -O-, at least two of X 16 to X 18 represent =N-, and X 13 is -NR When S-, at least one of X 16 to X 18 represents =N-, and R X each independently represents a hydrogen atom or a monovalent substituent.
In formula (1-4), X 19 to X 26 each independently represents =CR X - or =N-, at least two of X 19 to X 26 represent =N-, and R R represents a bonding site with another structure represented by *, a hydrogen atom or a monovalent substituent, and one of X 19 to X 26 is a bonding site with another structure represented by * In the group represented by formula (1-4), there is only one R x which is a bonding site with another structure represented by *.
The resin composition according to claim 1, wherein the compound A is a compound that decomposes under the action of light, heat, or a base to generate an aliphatic primary amine.
The compound a1 has at least one group selected from the group consisting of a protected primary amine structure, a group represented by formula (1-1), and a group represented by formula (1-2). The resin composition according to claim 1 or 2, which has a seed structure.
The resin composition according to claim 1 or 2, wherein the compound A is a compound represented by the following formula (A-2) or formula (A-3).

In formula (A-2), R 7 each independently represents an alkyl group that may have a substituent, a plurality of R 7 may be combined to form a ring structure, and R 8 is represented by formula ( At least one type selected from the group consisting of a group represented by any one of 1-1) to formula (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base, and a phenolic hydroxyl group. represents an organic group having a structure, and L 1 represents a single bond or a divalent linking group.
In formula (A-3), R 9 is a group represented by any one of formulas (1-1) to (1-4), an oxazole ring, a thiazole ring, a pyrimidine ring, a Schiff base group, and a phenolic group. represents an organic group having at least one type of structure selected from the group consisting of a hydroxyl group, and L 2 represents a single bond or a divalent linking group.
The resin composition according to claim 1 or 2, wherein the resin is polyimide or a polyimide precursor.
The resin composition according to claim 1 or 2, further comprising an aromatic heterocyclic compound different from the compound A.
The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator and a polymerizable compound.
The resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film for a rewiring layer.
A cured product obtained by curing the resin composition according to claim 1 or 2.
A laminate comprising two or more layers made of the cured product according to claim 9, and a metal layer between any of the layers made of the cured product.
A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 or 2 onto a base material to form a film.
The method for producing a cured product according to claim 11, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.
The method for producing a cured product according to claim 11, comprising a heating step of heating the film at 50 to 450°C.
A method for manufacturing a laminate, comprising the method for manufacturing a cured product according to claim 11.
A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 11.
A semiconductor device comprising the cured product according to claim 9.