JP7335964B2 - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, resin, and method for producing resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, a resin, and a method for producing a resin.

Polyimide is used in various applications because of its excellent heat resistance and insulating properties. The use is not particularly limited, but in the case of a semiconductor device for mounting, it can be used as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.

For example, in the applications described above, polyimide may be used in the form of a curable resin composition containing polyimide.
Since these curable resin compositions can be applied to a substrate or the like by a known coating method or the like, the degree of freedom in designing, for example, the shape, size, application position, etc. of the curable resin composition to be applied is high. It can be said that it is excellent in adaptability in manufacturing, such as high.
In addition to the high performance of polyimide, from the viewpoint of such excellent manufacturing adaptability, there are increasing expectations for the development of industrial applications of curable resin compositions containing polyimide.

For example, Patent Document 1 discloses a polyimide precursor obtained by reacting a tetracarboxylic dianhydride component and a diamine component, wherein the tetracarboxylic dianhydride component is a compound having a specific structure, polyimide Precursors have been described.
Further, Patent Document 2 describes a photosensitive resin composition containing (A) a polyamic acid having a specific structural unit, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. there is

JP 2014-172994 A JP 2009-251451 A

In a curable resin composition containing polyimide, it is desired to provide a curable resin composition that gives a cured film having excellent chemical resistance.

One embodiment of the present invention is a curable resin composition having excellent chemical resistance of the cured film obtained, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film An object of the present invention is to provide a manufacturing method and a semiconductor device including the cured film or the laminate.
Another object of the present invention is to provide a novel resin and a method for producing the resin.

Examples of representative embodiments of the present invention are described below.
<1> including a resin having a repeating unit represented by the following formula (1-1) and a solvent,
A curable resin composition.
In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. group, n represents an integer of 1 or more, and ^Q1 represents a divalent linking group.
<2> The curable resin composition according to <1>, wherein ^A1 is a group containing an ethylenically unsaturated bond, a cyclic ether group, or a methylol group as a polymerizable group.
<3> The curable resin composition according to <1> or <2>, further comprising a polymerization initiator and a polymerizable compound.
<4> The curable resin composition according to <1> or <2>, further comprising an acid generator and an acid crosslinking agent.
<5> Any of <1> to <4>, wherein Q ¹ contains at least one structure selected from the group consisting of structures represented by the following formulas (A-1) to (A-5) The curable resin composition according to any one of the above.
In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom; , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, a halogen atom, or a group containing a polymerizable group, L ^A31 and L ^A41 each independently represent a single bond, a carbonyl group , a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group, * each independently represents a binding site to another structure represents
<6> The curable resin composition according to any one of <1> to <5>, wherein Q ¹ contains a group containing a polymerizable group.
<7> The curable resin composition according to any one of <1> to <6>, wherein Y ¹ is an n+2-valent hydrocarbon group.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for rewiring layers.
<9> A cured film obtained by curing the curable resin composition according to any one of <1> to <8>.
<10> A laminate having two or more layers of the cured film according to <9> and having a metal layer between any of the cured films.
<11> A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of <1> to <8> to a substrate to form a film.
<12> The method for producing a cured film according to <11>, comprising the step of heating the film at 50 to 450°C.
<13> A semiconductor device comprising the cured film according to <9> or the laminate according to <10>.
<14> A resin having a repeating unit represented by the following formula (1-1).
In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. group, n represents an integer of 1 or more, and ^Q1 represents a divalent linking group.
<15> A production method for producing the resin according to <14>,
A compound A having at least two hydroxy groups and at least one reactive group is reacted with a compound B having a group capable of forming a bond with the reactive group and a polymerizable group to form a diol compound. the step of obtaining
A step of reacting the diol compound with a compound having three carboxy groups or a derivative of the compound having three carboxy groups to obtain a tetravalent carboxylic acid compound having two ester bonds;
A step of reacting the tetravalent carboxylic acid compound with a diamine compound to obtain a polyimide precursor, and
A method for producing a resin, comprising imidizing the polyimide precursor.

According to one embodiment of the present invention, a curable resin composition that provides a cured film having excellent chemical resistance, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. A film manufacturing method and a semiconductor device including the cured film or laminate are provided.
Moreover, according to another embodiment of the present invention, a novel resin and a method for producing the resin are provided.

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

(Curable resin composition)
The curable resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") contains a resin having a repeating unit represented by the following formula (1-1) and a solvent.
In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. group, n represents an integer of 1 or more, and ^Q1 represents a divalent linking group.

The curable resin composition of the present invention preferably further contains a polymerization initiator and a polymerizable compound, and more preferably further contains a radical photopolymerization initiator and a radically polymerizable compound.
Moreover, the curable resin composition of the present invention preferably further contains an acid generator and an acid cross-linking agent, and more preferably further contains a photoacid generator and an acid cross-linking agent.
The curable resin composition of the present invention may be a negative curable resin composition or a positive curable resin composition.
The term "negative curable resin composition" refers to a composition in which, when a layer formed from the curable resin composition is exposed to light, the unexposed portions (non-exposed portions) are removed by a developer. A layer formed from such a curable resin composition is called a negative curable resin composition layer.
A positive curable resin composition refers to a composition from which, when a layer formed from the curable resin composition is exposed to light, the exposed portion (exposed portion) is removed by a developer. A layer formed from such a curable resin composition is referred to as a positive curable resin composition layer.
By further including a polymerization initiator and a polymerizable compound, the curable resin composition can be, for example, a negative curable resin composition.
In addition, by further including a photoacid generator and an acid cross-linking agent, the curable resin composition can be, for example, a negative curable resin composition.
Furthermore, the curable resin composition further contains a photoacid generator, a radical polymerization initiator (preferably a thermal radical polymerization initiator) and a radically polymerizable compound, or further contains a photoacid generator and an acid crosslinking agent. Thus, for example, a positive curable resin composition can be obtained. In these embodiments, for example, alkali development is performed after exposure, and the pattern is cured by heating or the like after development, thereby forming a positive pattern from which the exposed portion is removed.

A cured film obtained from the curable resin composition of the present invention is excellent in chemical resistance.
Although the mechanism by which the above effects are obtained is not clear, it is presumed as follows.

The curable resin composition of the present invention contains a resin having a repeating unit represented by formula (1-1) (hereinafter also referred to as "specific resin").
Here, unlike conventional polyimide resins, the specific resin has an ester bond in the repeating unit represented by formula (1-1) and a polymerizable group between the ester bonds.
By adopting such an aspect, the amount of highly reactive polymerizable groups contained in the resin can be increased, so that the crosslink density in the cured film (the density of the crosslinked structure formed by crosslinking of the polymerizable groups) increases. , it is presumed that a cured film having excellent chemical resistance can be obtained.
Due to the excellent chemical resistance of the cured film, for example, on the cured film obtained by curing the curable resin composition of the present invention, another curable resin composition containing a solvent is further applied and cured to form a laminate. Even if the cured film comes into contact with a developing solution or other curable resin composition in the case of creating a , it is thought that the dissolution of the cured film is suppressed.
According to the present invention, for example, polar solvents such as dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, or the polar solvent and the alkaline aqueous solution It is thought that a cured film having excellent chemical resistance and having suppressed solubility in a mixed solution of No.
In addition, it is believed that the introduction of the ester bond into the resin improves the transparency of the resin. Therefore, when a curable resin composition layer is formed using a composition containing the above resin, and a patterned cured film is formed by pattern exposure and development, it is believed that pattern resolution is likely to be improved.
Furthermore, when the curable resin composition layer is a negative-type curable resin composition layer, it is believed that the exposure light can be easily transmitted due to the improved transparency of the resin. Therefore, in cross-linking by exposure, the cross-linking density in the cured film is increased, and a cured film having excellent chemical resistance is more likely to be obtained.
In addition, when the curable resin composition layer is a negative curable resin composition layer, it is believed that the exposure light can easily reach deep into the curable resin composition layer due to the improved transparency of the resin. Therefore, it is considered that the cross-linking density is increased especially in the deep part of the cured film, and a cured film having excellent chemical resistance in the deep part of the cured film is easily obtained. Here, the deep portion of the curable resin composition layer refers to a portion of the curable resin composition layer opposite to the exposed side, and the curable resin composition layer is formed on the substrate, and the substrate When exposure is performed from the opposite side, the portion of the curable resin composition layer on the substrate side is referred to as the deep portion of the curable resin composition layer. That is, according to the curable resin composition of the present invention, for example, when exposure is performed from the side opposite to the substrate, a cured film having excellent chemical resistance in the portion of the curable resin composition layer on the substrate side is formed. likely to be obtained easily.

Here, Patent Documents 1 and 2 neither describe nor suggest a resin having a repeating unit represented by formula (1-1). Moreover, in the curable resin composition in Patent Documents 1 and 2, there is a problem that the chemical resistance of the resulting cured film is low.

<Specific resin>
The curable resin composition of the present invention contains a specific resin.
The specific resin has a repeating unit represented by formula (1-1).
The specific resin may have a repeating unit represented by formula (1-1) in its side chain, but preferably has a repeating unit represented by formula (1-1) in its main chain.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.

[Repeating unit represented by formula (1-1)]
-X ¹ , X ² -
In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, and represent an aromatic hydrocarbon group from the viewpoint of chemical resistance and solvent solubility. is preferred.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. More preferred is a structure in which three hydrogen atoms are removed from a benzene ring.
The aliphatic cyclic group is preferably an aliphatic cyclic group having 6 to 30 carbon atoms, more preferably an aliphatic cyclic group having 6 to 20 carbon atoms, and still more preferably an aliphatic cyclic group having 6 to 10 carbon atoms. A structure obtained by removing three hydrogen atoms from an alicyclic structure, which is a membered ring structure, is more preferable.
The aliphatic cyclic group may be either a saturated aliphatic cyclic group or an unsaturated aliphatic cyclic group, but is preferably a saturated aliphatic cyclic group.
The aliphatic cyclic group may be either an aliphatic hydrocarbon cyclic group or an aliphatic heterocyclic group, but is preferably an aliphatic hydrocarbon cyclic group.
Among these, a saturated aliphatic hydrocarbon group is preferable as the aliphatic ring group.

In the aromatic hydrocarbon group or aliphatic cyclic group that is X ¹ or X ² , the two sites that bind to the imide structure in formula (1-1) are adjacent positions in the aromatic hydrocarbon group or aliphatic cyclic group. is preferably present in
As used herein, two bonding sites are present at adjacent positions in a ring structure means that the ring member in the ring structure in which a certain bonding site exists and the ring member in the ring structure in which another bonding site exists, Adjacent ring members in a ring structure. For example, when the ring structure is a benzene ring structure, the adjacent position is the ortho position.

Further, from the viewpoint of developability and solvent solubility, the repeating unit represented by formula (1-1) can be represented by any of the following formulas (1-2-1) to (1-2-6). is preferably a repeating unit represented by formula (1-2-1) or formula (1-2-2), more preferably a repeating unit represented by formula (1-2-1) It is further preferred that the repeating unit is a
In formulas (1-2-1) to (1-2-6), Y ¹ , A ¹ , n, and Q ¹ are respectively Y ¹ , A ¹ , n, and Q ¹ in formula (1-1) is synonymous with, and preferred embodiments are also the same.

-A ^1-
In formula (1-1), A ¹ represents a group containing a polymerizable group.
As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferable, and a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl A group, an epoxy group, an oxetanyl group, or a methylol group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, or a methylol group is even more preferred.
The number of polymerizable groups contained in A ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, One or two is particularly preferred, and one is most preferred.

Further, A ¹ is preferably a group represented by the following formula (P-1).
In formula (P-1), L ¹ represents a single bond or an m+1 valent linking group, A ² represents a polymerizable group, m represents an integer of 1 or more, and * represents a binding site with Y ^1. .
In formula (P-1), L ¹ is preferably a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, —NR ^N —, or a group in which two or more of these are bonded, and a single A bond, a hydrocarbon group, an ether bond, a carbonyl group, —NR ^N —, or a group in which two or more of these are bonded is more preferred.
^RN represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.
The hydrocarbon group for L ¹ is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by these bonds.

In formula (P-1), ^A2 is a vinyl group, (meth)allyl group, (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group. A (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, or a methylol group is more preferable.

In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 5, and 1 or 2 is particularly preferred, and 1 is most preferred.

Further, A ¹ is preferably a group represented by formula (P-2) or formula (P-3) below.
In formula (P-2), A ² represents a polymerizable group, and * represents a bonding site with Y ¹ .
In formula (P-2), A ² has the same definition as A ² in formula (P-1), and preferred embodiments are also the same.
In formula (P-3), A ² represents a polymerizable group, L ² is a hydrocarbon group, or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, a carbonate bond, -NR ^N - or a group in which two or more of these are bonded, ^Z1 represents an ether bond, an ester bond, a urethane bond, a urea bond, a carbonate bond, or an amide bond, and * represents a bonding site with ^Y1 . ^RN is as described above.
In formula (P-3), A ² has the same definition as A ² in formula (P-1), and preferred embodiments are also the same.
In formula (P-3), L ² is preferably a hydrocarbon group, a (poly)alkyleneoxy group, or a group represented by a combination thereof, more preferably a hydrocarbon group.
As used herein, a (poly)alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, more preferably an alkylene group.
The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
In the present invention, when simply described as "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl group", "alkylene group" and the like, unless otherwise specified, these groups refer to branched structures and cyclic At least one of the structures may be provided. For example, unless otherwise specified, the term "alkyl group" includes linear alkyl groups, branched alkyl groups, cyclic alkyl groups, and alkyl groups represented by combinations thereof.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenylene group or a naphthylene group, and a phenylene group. Especially preferred.
The alkylene group in the (poly)alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group. .
Further, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 5, and particularly 2 to 4. preferable.
In formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond or an amide bond, more preferably an ester bond, a urethane bond, a urea bond or an amide bond.
In the present invention, when simply described as "ester bond", "urethane bond", "amide bond", etc., the direction of these bonds is not limited. For example, when Z ¹ is an ester bond, the bonding site of Z ¹ with L ² may be a carbon atom or an oxygen atom in the ester bond.

From the viewpoint of chemical resistance, the distance between the polymerizable group contained in A ¹ and the main chain of the polyimide is preferably 0-15, more preferably 0-5.
Here, the distance between the polymerizable group contained in A ¹ and the main chain of the polyimide is the minimum number of atoms contained between the atoms contained in the main chain of the polyimide and the polymerizable group. Say. For example, in the resin represented by the formula (PA-1) in Examples described later, the distance between the methacrylamide group and the main chain is 0, and the distance between the methacryloxy group and the polyimide main chain is 1. Further, in the resin represented by the formula (PA-3) in the examples described later, the distance between the methacryloxy group bonded to the main chain by the urea bond and the polyimide main chain is 5, and the urethane bond is used to bond to the main chain. The distance between the methacryloxy group and the main chain of polyimide is 6. Further, in the resin represented by the formula (PA-4) in the examples described later, the distance between the two acrylamide groups and the polyimide main chain is zero. That is, when the polyimide has a ring structure inside the main chain, the "atoms contained in the above-described main chain of the polyimide" include ring members of the ring structure.
Further, when A ¹ contains a plurality of polymerizable groups, among the polymerizable groups contained in A ¹ , the distance between the polymerizable group closest to the main chain and the main chain of the polyimide is preferably 0 to 15. Preferably, 0 to 5 is more preferable. Furthermore, when A ¹ contains a plurality of polymerizable groups, the distance between all the polymerizable groups contained in A ¹ and the main chain of the polyimide is more preferably 0 to 15, more preferably 0 to 5. is particularly preferred.

-n-
In formula (1-1), n represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and an integer of 1 to 4. Preferably, 1 or 2 is particularly preferred, and 2 is most preferred.
Also, when n is an integer of 2 or more, n A ¹ may be the same or different.

-Y ¹ -
Y ¹ represents an n+2-valent organic group, preferably a hydrocarbon group.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and has 1 to 10 carbon atoms. is more preferably a saturated aliphatic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by these bonds.
Y ¹ preferably includes, for example, structures represented by the following formulas (Y-1) to (Y-4). In the following formulas (Y-1) to (Y-4), * respectively represents the bonding site with the oxygen atom in the ester bond in formula (1-1), and # represents A in formula (1-1). represents the binding site with ¹ .
In formula (Y-1) or formula (Y-2), L ^Y1 and L ^Y2 each independently represent an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. More preferred is a methylene group.
In formula (Y-3) or formula (Y-4), each L ^Y4 independently represents a single bond or a divalent hydrocarbon group, preferably a single bond. The divalent hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
In formula (Y-4), L ^Y3 is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C(=O)-, - It is preferably S—, —S(=O) ₂ —, —NHC(=O)—, or a group in which two or more of these are combined, and has 1 carbon atom optionally substituted with a single bond or a fluorine atom. to 3 alkylene groups, -O-, -C(=O)-, -S- or -S(=O) ₂ -, more preferably -CH ₂ -, -O-, -S-, It is more preferably a divalent group selected from the group consisting of -S(=O) ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ -.
In formula (Y-3) or formula (Y-4), each n independently represents an integer of 1 to 4, preferably 1 or 2, more preferably 1.

- Q ¹ -
In formula (1-1), Q ¹ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR ^N - It is preferably a group in which at least one is bonded. ^RN is as described above.
The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 2 to 30 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.
Among these, from the viewpoint of solvent solubility, Q ¹ is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and is preferably a group containing an aromatic hydrocarbon ring group. more preferred.

Also, Q ¹ preferably contains a group containing a polymerizable group.
As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferable, and a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl A group, an epoxy group, an oxetanyl group, or a methylol group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, or a methylol group is even more preferred.
The number of polymerizable groups contained in Q ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, One or two is particularly preferred, and one is most preferred.
The group containing a polymerizable group in Q ¹ is preferably a group represented by the above formula (P-1), more preferably a group represented by the above formula (P-2) or (P-3). Preferred is the group represented by formula (P-3).

In addition, Q ¹ preferably contains at least one structure selected from the group consisting of structures represented by any of the following formulas (A-1) to (A-5), and the following formula ( A-1) to the structure represented by any one of the following formulas (A-5) are more preferable.

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom; , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, a halogen atom, or a group containing a polymerizable group, and L ^A31 and L ^A41 each independently represent a single bond, carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group; represents the part.

From the viewpoint of chemical resistance, among these, ^Q1 should have a structure represented by formula (A-1), formula (A-2), formula (A-3) or formula (A-4). is preferred.

In formula (A-1), R ^A11 to R ^A14 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom, or a group containing a polymerizable group. An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a group containing a polymerizable group is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
The group containing the polymerizable group in R ^A11 to R ^A14 is preferably a group represented by the above formula (P-1), and is represented by the above formula (P-2) or formula (P-3). is more preferred, and the group represented by formula (P-3) is even more preferred.
Examples of the halogen atom in the halogenated alkyl group of R ^A11 to R ^A14 or the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom or a bromine atom being preferred.

In formula (A-2), R ^A21 to R ^A24 have the same meanings as R ^A11 to R ^A14 in formula (A-1), respectively, and preferred embodiments are also the same.

In formula (A-3), R ^A31 to R ^A38 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom, or a group containing a polymerizable group. An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a group containing a polymerizable group is more preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.
The halogen atom in the halogenated alkyl group in R ^A31 to R ^A38 or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferable.
The group containing the polymerizable group in R ^A31 to R ^A38 is preferably a group represented by the above formula (P-1), and is represented by the above formula (P-2) or formula (P-3). is more preferred, and the group represented by formula (P-3) is even more preferred.
In formula (A-3), L ^A31 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S -, -NR ^N -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group is preferred, and a single bond or -O- is more preferred.
^RN represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.
The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group. It is preferably a group.
As the heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is preferable, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is preferable, a pyrrolidine ring, A group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholine ring is more preferred. These heterocycles may further form a condensed ring with another heterocycle or hydrocarbon ring.
The heterocyclic ring preferably has 5 to 10 ring members, more preferably 5 or 6 members.
Moreover, the hetero atom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.

In formula (A-4), R ^A41 to R ^A48 and L ^A41 have the same meanings as R ^A31 to R ^A38 and L ^A31 in formula (A-3), respectively, and preferred embodiments are also the same.

In formula (A-5), R ^A51 to R ^A58 have the same definitions as R ^A11 to R ^A14 in formula (A-1), and preferred embodiments are also the same.

Further, in formulas (A-1) to (A-5), * is preferably each independently a binding site to the main chain in the resin.

Q ¹ in formula (1-1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of the flexibility of the resulting cured film. Each Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L ⁰ has the same definition as L ^A31 in (A-3) above, and preferred embodiments are also the same.

Q ¹ in formula (1-1) is preferably a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-line transmittance. In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.

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, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and each * independently represents a binding site to another structure.

The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. Each * independently represents a binding site with another structure.

-Carboxylic acid dianhydride, diamine compound-
The repeating unit represented by formula (1-1) is derived from a carboxylic acid dianhydride represented by formula (1-3) below or a diamine compound represented by formula (1-4) below. It is preferable to have a structure that
In formula (1-3), X ¹ , Y ¹ , A ¹ , n and X ² are respectively synonymous with X ¹ , Y ¹ , A ¹ , n and X ² in formula (1-1), A preferred embodiment is also the same.
In formula (1-4), Q ¹ has the same meaning as Q ¹ in formula (1-1), and preferred embodiments are also the same.

Examples of the carboxylic acid dianhydride represented by the formula (1-3) include anhydrides (AA-1) to (AA-6), anhydrides (AA-8), etc. used in Examples described later. mentioned.
Moreover, you may use the carboxylic dianhydride which has a reactive group as a carboxylic dianhydride.
Examples of the reactive group include a carboxy group, a carboxy halide group, a hydroxy group, an amino group, an isocyanate group, and a cyclic ether group.
After reacting a carboxylic dianhydride having a reactive group with a diamine such as a diamine represented by the formula (1-4), the reactive group, a group that reacts with the reactive group, and polymerizability A resin having a repeating unit represented by formula (1-1) can be obtained by reacting it with a compound having a group.
For example, a carboxylic acid dianhydride having a reactive group (such as a carboxyl group), such as the anhydride (AA-7) in Examples described later, and a diamine such as the diamine represented by formula (1-4) After the reaction, by reacting with a compound having a group that reacts with the reactive group such as glycidol and a polymerizable group, a resin containing a repeating unit represented by formula (1-1) can also be obtained. It is possible.

Diamines represented by formula (1-4) include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; , 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 or isophoronediamine; meta- or para-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 '-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl (4,4′-diamino-2,2′-dimethylbiphenyl), 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis(4- amino-3-carboxyphenyl)methane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-amino phenyl)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′ -tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4 '-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl methane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylene Diamine, 4,6-dihydroxy-1,3-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-amino phenyl)ethane, diaminobenzanilide, diaminobenzoic acid, esters 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-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-( 3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5- dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(4-amino-2-trifluoromethylphenoxy ) benzene, 4,4′-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4′-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4′-bis( 4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4′-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3- trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3′,5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis(trifluoromethyl) At least one diamine selected from biphenyl, 2,2',5,5',6,6'-hexafluorotolysine and 4,4'-diaminoquaterphenyl.

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

Diamines having at least two alkylene glycol units in the main chain are also preferred examples. Preferred are diamines containing two or more of ethylene glycol chains and/or propylene glycol chains in one molecule, and more preferred are diamines containing no aromatic ring. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 1-(2-(2-(2 -aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine and the like. not.

Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

Diamine compounds that give the structure of formula (51) or (61) above include dimethyl-4,4'-diaminobiphenyl and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. , 2,2′-bis(fluoro)-4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more may be used in combination.

In addition, for the purpose of improving adhesion to the substrate, a diamine having a siloxane structure such as bis(3-aminopropyl)tetramethyldisiloxane and bis(para-aminophenyl)octamethylpentasiloxane may be used as the diamine component. good.

In addition, the following diamines can also be preferably used.

- Content of repeating unit represented by formula (1-1) -
The content of the repeating unit represented by formula (1-1) in the specific resin is not particularly limited, but is preferably 10% by mass or more, and 20% by mass or more, relative to the total mass of the specific resin. is more preferable, and 30% by mass or more is even more preferable. The upper limit of the content is not particularly limited, and may be 100% by mass or less.
Further, as one aspect of the specific resin, it is also preferable to employ an aspect in which the repeating unit represented by formula (1-1) is contained in a high content.
In this case, the content of the repeating unit represented by formula (1-1) is preferably 50% by mass or more, more preferably 60% by mass or more, relative to the total mass of the specific resin. It is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. The upper limit of the content is not particularly limited, and may be 100% by mass or less.
The specific resin may contain a single type of repeating unit represented by formula (1-1), or may contain two or more types of repeating units represented by formula (1-1) having different structures. When the specific resin contains two or more repeating units represented by formula (1-1) having different structures, the total content of all repeating units represented by formula (1-1) contained in the specific resin is , is preferably included in the above content range.

[Other repeating units]
The specific resin may further contain other repeating units.

- Repeating unit represented by any one of formulas (2-1) to (2-3) -
Other repeating units include repeating units represented by any of the following formulas (2-1) to (2-3).
When the specific resin contains a repeating unit represented by any of the following formulas (2-1) to (2-3), the specific resin is any of the following formulas (2-1) to (2-3) It is preferable that the main chain contains a repeating unit represented by.
In formulas (2-1) to (2-3), X ¹ , Y ¹ , A ¹ , X ² , n and Q ¹ are respectively X ¹ , Y ¹ and A ¹ in formula (1-1) , X ² , n and Q ¹ , and preferred embodiments are also the same.
In formulas (2-1) to (2-3), A ^A1 , A ^A2 , R ¹¹³ and R ¹¹⁴ are respectively synonymous with A ^A1 , A ^A2 , R ¹¹³ and R ¹¹⁴ in formula (1) described later. The same applies to preferred embodiments.

<<Content>>
The total content of repeating units represented by any one of formulas (2-1) to (2-3) in the specific resin is not particularly limited, but is 30% by mass or less with respect to the total mass of the specific resin. is preferably 20% by mass or less, and even more preferably 10% by mass or less. The lower limit of the above total content is not particularly limited, and may be 0% by mass or more.
Further, from the viewpoint of the chemical resistance of the cured film to be obtained, as one mode of the specific resin, the mode substantially does not contain the repeating units represented by the formulas (2-1) to (2-3). is also preferred.
In this case, the total content of the repeating units represented by any of formulas (2-1) to (2-3) is preferably 5% by mass or less with respect to the total mass of the specific resin. It is more preferably 3% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The specific resin may contain a single repeating unit represented by any one of the formulas (2-1) to (2-3), or may contain different structural formulas (2-1) to (2- It may contain two or more repeating units represented by any one of 3). When the specific resin contains two or more types of repeating units represented by any of formulas (2-1) to (2-3) having different structures, all formulas (2-1) to It is preferable that the total content of the repeating units represented by formula (2-3) is within the above range.

-Repeating unit represented by formula (4)-
The specific resin may further contain a repeating unit represented by formula (4).
When the specific resin contains a repeating unit represented by the following formula (4), the specific resin preferably contains a repeating unit represented by the following formula (4) in its main chain.
However, the repeating unit represented by formula (1-1) above does not fall under the repeating unit represented by formula (4).
In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.

Examples of the divalent organic group represented by R ¹³¹ include the same groups as Q ¹ in formula (1-1), and the preferred range is also the same.

R ¹³² is preferably a tetravalent organic group containing an aromatic ring, more preferably a group represented by the following formula (5) or (6).

R ¹¹² is a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or 6 to 6 carbon atoms which may have a substituent. 20 aromatic hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHC(=O)-, or a combination of two or more of these is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a phenylene group which may have a substituent, -O-, -C(=O)-, A group selected from -S- and S(=O) ₂ - is more preferable, and -CH ₂ -, a phenylene group optionally having a substituent, -O-, -C(=O)- , -S-, -S(=O) ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - are more preferably divalent groups selected from the group consisting of . Each * independently represents a binding site with another structure.

As R ¹³² , a tetravalent organic group represented by the following formula (R-1) is also preferred.
In formula (R-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2-valent organic group, and X ^R1 each independently represents a substituted group, n represents an integer of 0 or more, and * independently represents a binding site to another structure.

In formula (R-1), X ¹ , X ² , Y ¹ and n are respectively synonymous with X ¹ , X ² , Y ¹ and n in formula (1-1), and preferred embodiments are also the same. . However, the description of “bonding site with A ^{1 in formula (1-1)” in the description of Y 1 in} formula (1-1) should read “bonding with X ^R1 or hydrogen atom in formula (R-1) shall be read as "part".

In formula (R-1), each X ^R1 is preferably independently a substituent containing no polymerizable group. Examples of the polymerizable group include the polymerizable groups described for A ¹ in formula (1-1) above.
Examples of substituents that do not contain a polymerizable group include an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, or a phosphonic acid group. It is preferably a group.
From the standpoint of alkali developability, X ^R1 is preferably a phenolic hydroxy group, a carboxy group, or a sulfo group, more preferably a carboxy group.
From the viewpoint of solvent solubility, X ^R1 is preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

Specific examples of the tetravalent organic group represented by R ¹³² in formula (4) include a tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same definition as R ¹³² in formula (4).

Specific examples of the tetracarboxylic dianhydride include anhydride (AA-7), pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyl in the examples described later. tetracarboxylic dianhydride, 3,3′,4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic 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, 4,4′ -(Hexafluoroisopropylidene)diphthalic 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 their C1-C6 alkyl derivatives and C1-C6 alkoxy At least one selected from derivatives is exemplified.

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

<<Content>>
The content of the repeating unit represented by formula (4) in the specific resin is not particularly limited, but is preferably 90% by mass or less, more preferably 80% by mass or less, relative to the total mass of the specific resin. It is preferably 70% by mass or less, and more preferably 70% by mass or less. The lower limit of the above total content is not particularly limited, and may be 0% by mass or more.
In addition, from the viewpoint of chemical resistance of the cured film to be obtained and from the viewpoint of improving the transparency of the resin, as one aspect of the specific resin, the content of the repeating unit represented by formula (4) is low. A certain aspect is also preferable.
In this case, the content of the repeating unit represented by formula (4) is preferably 50% by mass or less, more preferably 30% by mass or less, and 20% by mass with respect to the total mass of the specific resin. % or less, and particularly preferably 10 mass % or less. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The specific resin may contain a single type of repeating unit represented by formula (4), or may contain two or more types of repeating units represented by formula (4) having different structures. When the specific resin contains two or more types of repeating units represented by formula (4) having different structures, the total content of all repeating units represented by formula (4) contained in the specific resin is the above content is preferably included in the range of

-Repeating unit represented by formula (1)-
The specific resin may further contain a repeating unit represented by the following formula (1).
When the specific resin contains a repeating unit represented by the following formula (1), the specific resin preferably contains a repeating unit represented by the following formula (1) in its main chain.
In formula (1), A ^A1 and A ^A2 each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.
Also, one of the structures containing two amide groups described in the repeating unit represented by formula (1) may be imide-cyclized.
Examples of the structure in which one of the above is imide-cyclized include the following formula (1-A) and the following formula (1-B).
In formula (1-A) or formula (1-B), A ^A1 , A ^A2 , R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ are respectively A ^A1 , A ^A2 , R ¹¹¹ in formula (1), It has the same meaning as R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ , and the preferred embodiments are also the same.

In formula (1), A ^A1 and A ^A2 each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, both of which are polymerizable It is more preferred to contain a group.
Examples of the polymerizable group for R ¹¹³ or R ¹¹⁴ include the same groups as the polymerizable group for A ¹ in formula (1-1) above.

R ¹¹³ or R ¹¹⁴ is also preferably a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by the following formula (III).

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

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, or a (poly)alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group having 1 carbon 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred; the repeating number is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3).
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. alkylene groups such as -CH ₂ CH(OH)CH ₂ -, and more preferred are ethylene group, propylene group, trimethylene group and -CH ₂ CH(OH)CH ₂ -.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
In formula (III), * represents a binding site with another structure.
In preferred embodiments, the monovalent organic group for R ¹¹³ or R ¹¹⁴ in formula (1) is an aliphatic group, an aromatic group and an arylalkyl group having 1, 2 or 3, preferably 1 acid group. etc. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxy group.
As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves solubility in a developer is preferably used.

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

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more in the case of cyclic). Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. are mentioned. Moreover, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

Specific examples of aromatic groups include substituted or unsubstituted aromatic hydrocarbon groups (cyclic structures constituting the group include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group ( The cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, and a benzofuran. ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring , xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring).

In formula (1), R ¹¹⁵ has the same definition as R ¹³² in formula (4), and preferred embodiments are also the same.
In formula (1), R ¹¹¹ has the same definition as Q ¹ in formula (1-1) above, and preferred embodiments are also the same.

<<Content>>
The total content of the repeating units represented by formula (1) in the specific resin is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total mass of the specific resin. More preferably, it is 10% by mass or less. The lower limit of the above total content is not particularly limited, and may be 0% by mass or more.
From the viewpoint of the chemical resistance of the cured film to be obtained, it is also preferable to adopt an embodiment in which the repeating unit represented by formula (1) is not substantially contained as one embodiment of the specific resin.
In this case, the total content of the repeating units represented by formula (1) is preferably 5% by mass or less, more preferably 3% by mass or less, relative to the total mass of the specific resin. % by mass or less is more preferable. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The specific resin may contain a single type of repeating unit represented by formula (1), or may contain two or more types of repeating units represented by formula (1) having different structures. When the specific resin contains two or more types of repeating units represented by formula (1) having different structures, the total content of all repeating units represented by formula (1) contained in the specific resin is the above content is preferably included in the range of
Further, when the specific resin contains a repeating unit represented by formula (1-A) or formula (1-B), the repeating unit represented by formula (1), represented by formula (1-A) The total content of the repeating units and the repeating units represented by formula (1-B) is preferably within the above content range.

-Terminal structure-
The terminal structure of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, the terminal may be monoamine, monoalcohol, phenol, thiol, thiophenol, acid anhydride, monocarboxylic acid, monoacid chloride compound, It may be blocked with a terminal blocking agent such as a monoactive ester compound. Among these terminal blockers, monoamine is preferably used. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantane alcohol and other tertiary alcohols, and the like. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like. Monoamines 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-amino naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid , 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
Moreover, when blocking the amino group at the terminal of the resin, it is possible to block with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and the like. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.

〔Content〕
The content of the specific resin in the curable resin composition of the present invention, from the viewpoint of improving the breaking elongation of the resulting cured film, with respect to the total solid content of the curable resin composition, it is 20 wt% or more. It is preferably 30% by mass or more, more preferably 40% by mass or more.
From the viewpoint of improving the resolution of the curable resin composition, the upper limit of the content is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[Physical properties of specific resin]
-molecular weight-
The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and further preferably 10,000 to 100,000. preferable.
The number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, even more preferably 4,000 to 50,000.
Moreover, as a preferable aspect of the present invention, there is an aspect using a specific resin having a large molecular weight. According to the above aspect, a cured film having excellent film strength can be obtained.
Mw of the specific resin used in the above embodiment is preferably 40,000 or more, more preferably 50,000 or more, still more preferably 60,000 or more, and 70,000 or more. is particularly preferred, and 80,000 or more is most preferred. Although the upper limit of Mw is not particularly limited, it is preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less.
Further, Mn of the specific resin used in the above embodiment is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 18,000 or more, and 20,000 or more. 1 is particularly preferred, and 25,000 or more is most preferred. Although the upper limit of Mn is not particularly limited, it is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.
The molecular weight distribution of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the molecular weight dispersity refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

- Acid value -
When the curable resin composition is used for solvent development, which will be described later, the acid value of the specific resin is preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, and more preferably 0.3 mmol/g. is more preferable. The lower limit of the acid value is not particularly limited, and may be 0 mmol/g or more.
When the curable resin composition is used for alkali development, which will be described later, the acid value of the specific resin is preferably 1.2 to 7 mmol/g, more preferably 1.5 to 6 mmol/g. More preferably ~5 mmol/g.
In the present invention, the acid value refers to the amount (mmol) of acid groups contained in 1 g of the specific resin.
An acid group refers to a group that is neutralized by an alkali of pH 12 or higher (for example, sodium hydroxide). Moreover, the acid group is preferably a group having a pKa of 10 or less.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
In the specific resin, the acid group is, for example, Q ¹ in the repeating unit represented by formula (1-1), X ^R1 in the repeating unit represented by formula (4), Included in R ¹³¹ etc. in
Examples of the acid group include a phenolic hydroxy group, a carboxy group, and a sulfo group, with the carboxy group being preferred.

-Polymerizable group-
The molar amount of the polymerizable group contained in 1 g of the specific resin (polymerizable group value, unit: mol/g) is preferably 0.05 to 10 mol/g, more preferably 0.1 to 6 mol/g. is more preferred.
The polymerizable group is included, for example, in A ¹ and Q ¹ in the repeating unit represented by formula (1-1), R ¹³¹ in the repeating unit represented by formula (4), and the like.
When the specific resin contains an ethylenically unsaturated bond as a polymerizable group, the molar amount of the ethylenically unsaturated bond contained in 1 g of the specific resin is preferably 0.05 to 10 mol / g, and 0.1 to More preferably 6 mol/g.
When the specific resin contains a polymerizable group such as a cyclic ether group or a methylol group as a polymerizable group, the molar amount of the polymerizable group contained in 1 g of the specific resin is preferably 0.05 to 10 mol/g. , more preferably 0.1 to 6 mol/g.

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

- Fluorine atomic weight -
From the viewpoint of film strength of the resulting cured film, the specific resin preferably has a fluorine atom.
The amount of fluorine atoms relative to the total mass of the specific resin is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.
The fluorine atom is, for example, Q ¹ in the repeating unit represented by formula (1-1), R ¹³² in the repeating unit represented by formula (4), or R in the repeating unit represented by formula (4) ¹³¹ , Q ¹ in the repeating unit represented by formula (1-1), R ¹³² in the repeating unit represented by formula (4), or the repeating unit represented by formula (4) It is more preferably contained as a fluorinated alkyl group in R ¹³¹ in .

〔Concrete example〕
Specific examples of the specific resin include the specific resins used in Examples described later.

〔Production method〕
The specific resin is produced, for example, by the synthetic method shown in the synthetic examples in the examples below.

Specifically, the method for producing the resin used in the present invention includes a step of reacting a tetravalent carboxylic acid compound and a diamine compound to obtain a polyimide precursor (precursor production step), and It is preferable to include a step of imidizing (imidization step).

- Precursor manufacturing process -
In the precursor production step, a polyimide precursor is obtained by reacting a tetravalent carboxylic acid compound and a diamine compound.
The polyimide precursor is preferably a polyimide precursor containing a repeating unit represented by the above formula (2-3). Further, the polyimide precursor may contain a repeating unit represented by the above formula (1) in addition to the repeating unit represented by the formula (2-3).
The tetravalent carboxylic acid compound may be a carboxylic acid derivative in which at least one of the four carboxylic acids is modified by esterification, halogenation, etc. It may be an anhydride, preferably a carboxylic acid dianhydride.
Specifically, the carboxylic dianhydride represented by the above formula (1-3) or the carboxylic acid dianhydride represented by the above formula (7) is used. be able to. Further, as the tetravalent carboxylic acid compound, a compound having a structure obtained by hydrolyzing the carboxylic acid dianhydride, or a compound having a structure obtained by modifying the above compound by esterification, halogenation, etc. is used. be able to.
Specifically, the diamine compound represented by the above formula (1-4) can be used as the diamine compound.
In addition, the production of the precursor can be carried out with reference to known methods.

-Imidation process-
In the imidization step, the polyimide precursor obtained in the precursor production step is imidized to obtain a specific resin.
The imidization step may be any of thermal imidization (e.g., imidization by heating), chemical imidization (e.g., imidization using a catalyst), and imidization by a combination thereof. It is carried out by heating in the presence of a catalyst such as
Moreover, in the imidization step, for example, a dehydrating agent may be used. Examples of dehydrating agents include carboxylic acid anhydrides such as acetic anhydride.
In the production of the specific resin of the present invention, imidization is possible at a low heating temperature (for example, 80 ° C. to 150 ° C.), so the method of producing the specific resin of the present invention is also useful from the viewpoint of energy saving. It is believed that there is.
Other details of imidization can be carried out by known methods.

-Other processes-
The method for producing a resin of the present invention includes a compound A having at least two hydroxy groups and at least one reactive group, a group capable of forming a bond with the reactive group, and a compound having a polymerizable group. A step of reacting B to obtain a diol compound (diol production step), and reacting the diol compound with a compound having three carboxy groups or a derivative of the compound having three carboxy groups, It is preferable to further include a step of obtaining a tetravalent carboxylic acid compound having two ester bonds (a tetravalent carboxylic acid compound manufacturing step). Through these steps, the carboxylic acid dianhydride represented by the above formula (1-3) can be obtained.
In the precursor production step, it is preferable to use a tetravalent carboxylic acid compound having two ester bonds as the tetravalent carboxylic acid compound.

<<Diol manufacturing process>>
Examples of the reactive group in compound A used in the diol production process include, but are not particularly limited to, an amino group, a hydroxy group, a carboxy group, and the like.
The group capable of forming a bond with the reactive group in compound B is not particularly limited, but includes a hydroxy group, a carboxylic acid group, a carboxylic acid halide group, an epoxy group, an isocyanate group, and the like.
Examples of the polymerizable group in compound B include the groups exemplified as the groups included in A ¹ in formula (1-1) above.
The diol production process is carried out, for example, by carrying out the following steps (1) to (3).
(1) Step of protecting two hydroxy groups contained in compound A with a known protecting group (e.g., acetal protecting group, ether protecting group, acyl protecting group, silyl ether protecting group, etc.) (2) Compound Step of reacting the reactive group in A with a group capable of forming a bond with the reactive group in compound B to introduce a polymerizable group (3) Step of deprotecting the protecting group Reaction conditions in each step etc. may be appropriately determined with reference to known reaction conditions and the like.
Specifically, the step of synthesizing the intermediate (AA) in the examples described later corresponds to the above (1), the step of synthesizing the intermediate (AB) corresponds to the above (2), The step of synthesizing intermediates (AC) corresponds to (3) above.

<Manufacturing step of tetravalent carboxylic acid compound>>
In the tetravalent carboxylic acid compound production step, by reacting the diol compound obtained in the diol production step with a compound having three carboxy groups or a derivative of the compound having three carboxy groups, 2 A tetravalent carboxylic acid compound having two ester bonds is obtained.
The compound having three carboxy groups or the derivative of the compound having three carboxy groups includes a compound having three carboxy groups, a compound having one carboxy group and one carboxylic acid anhydride group, and one A compound having a carboxylic acid halide group and one carboxylic anhydride group, a compound having one carboxylic acid ester group and one carboxylic anhydride group, a compound having three carboxylic acid ester groups, one carboxylic acid Examples include compounds having a halide group and two carboxylic acid ester groups, and compounds having one carboxylic acid halide group and one carboxylic acid anhydride group are preferred.
The conditions and the like for the above reaction may be appropriately determined with reference to known esterification reactions.
Specifically, in the examples described later, the step of synthesizing the anhydride (AA-1) from the intermediate (AC) and trimellitic anhydride chloride corresponds to the tetravalent carboxylic acid compound production step.

-Other manufacturing methods-
The method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by heating and dehydrating the carboxylic acid dianhydride and the diamine compound during the reaction.
Carboxylic dianhydrides include, for example, carboxylic dianhydrides represented by formula (1-3). The carboxylic acid dianhydride represented by the above formula (1-3) is preferably a compound obtained in the above-described process for producing a tetravalent carboxylic acid compound.
As the diamine compound, the diamine compound represented by the above formula (1-4) can be used.
Furthermore, the method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by decarboxylating the carboxylic acid dianhydride and the diisocyanate compound at a high temperature during the reaction.
Carboxylic dianhydrides include, for example, carboxylic dianhydrides represented by formula (1-3). The carboxylic acid dianhydride represented by the above formula (1-3) is preferably a compound obtained in the above-described process for producing a tetravalent carboxylic acid compound.
Diisocyanate compounds include compounds in which the two amino groups in the compound represented by the above formula (1-4) are replaced with isocyanate groups.
For details of these production methods, reference can be made to known methods for synthesizing polyimides.

Further, the method for producing the resin used in the present invention includes a step of reacting a tetravalent carboxylic acid compound having a reactive group and a diamine compound to obtain a polyimide precursor, imidizing the polyimide precursor to reactive groups. and a step of reacting the resin, a group capable of forming a bond with the reactive group, and a compound C having a polymerizable group.

Examples of the reactive group include, but are not particularly limited to, an amino group, a hydroxy group, and a carboxy group.
In the tetravalent carboxylic acid compound having a reactive group, at least one of the four carboxylic acids may be a modified carboxylic acid derivative such as esterification or halogenation, or two carboxylic acids may be anhydrides. It may be a carboxylic acid dianhydride, preferably a carboxylic acid dianhydride.
As the carboxylic acid dianhydride having a reactive group, specifically, among the carboxylic acid dianhydrides represented by the above formula (7), a carboxylic acid dianhydride having a reactive group can be used. can. Further, as the tetravalent carboxylic acid compound, a compound having a structure obtained by hydrolyzing the carboxylic acid dianhydride, or a compound having a structure obtained by modifying the above compound by esterification, halogenation, etc. is used. be able to.
Moreover, you may use together the carboxylic acid dianhydride which does not have a reactive group.
Specifically, the diamine compound represented by the above formula (1-4) can be used as the diamine compound.

The group capable of forming a bond with the reactive group in compound C is not particularly limited, but includes a hydroxy group, a carboxylic acid group, a carboxylic acid halide group, an epoxy group, an isocyanate group, and the like.
For example, the polymerizable group in the above compound C includes the groups exemplified as the groups included in A ¹ in the above formula (1-1).

Further, the method for producing the resin used in the present invention includes reacting a compound having three carboxy groups or a derivative of the compound having three carboxy groups with a diamine compound or a diisocyanate compound to produce two imides. A production method including a step of obtaining a compound D having a ring structure and two carboxylic acids, and a step of reacting the compound D with a diol compound having a polymerizable group to obtain a resin.

The compound having three carboxy groups or the derivative of the compound having three carboxy groups includes a compound having three carboxy groups, a compound having one carboxy group and one carboxylic acid anhydride group, a compound having one carboxylic acid halide group and one carboxylic anhydride group, a compound having one carboxylic acid ester group and one carboxylic anhydride group, a compound having three carboxylic acid ester groups, one carboxylic acid Examples include compounds having an acid halide group and two carboxylic acid ester groups, and compounds having one carboxyl group and one carboxylic acid anhydride group are preferred.
Specifically, the diamine compound represented by the above formula (1-4) can be used as the diamine compound.
Specific examples of the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (1-4) are replaced with isocyanate groups.
The conditions and the like for the above reaction may be appropriately determined with reference to known imidization reactions.

Examples of the diol compound having a polymerizable group include compounds represented by the following formula (DO-1).
In formula (DO-1), Y ¹ , A ¹ and n have the same meanings as Y ¹ , A ¹ and n in formula (1-1), respectively, and preferred embodiments are also the same.
Moreover, you may use together the other diol compound which does not have a polymerizable group.
The reaction conditions in the step of obtaining the resin may be appropriately determined with reference to known polyester production methods.

As an example, a synthesis scheme for obtaining a resin having a structure similar to that of the polyimide (PA-1) in the examples by the above production method is shown below.

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

Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone , ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are preferred. .

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

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

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

Suitable sulfoxides include, for example, dimethyl sulfoxide.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N- Preferred examples include dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and the like.
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- 1 solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably an amount such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and an amount that is 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, more preferably from 20 to 70% by mass, and even more preferably from 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating and the method of application.

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

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

[Polyimide, polyamideimide (other resins)]
From the viewpoint of the film strength of the resulting cured film, the polyimide or polyamideimide, which is another resin, preferably has a repeating unit represented by the above formula (4).
In polyimide or polyamideimide, the number of repeating units represented by formula (4) may be one, or two or more. Polyimides or polyamideimides may also contain other types of repeating units in addition to the repeating units of formula (4) above.
For example, the polyamideimide preferably further contains a repeating unit containing an amide structure, or a repeating unit containing an amide structure and an imide structure.

As one embodiment of the polyimide or polyamideimide in the present invention, 50 mol% or more of all repeating units, further 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by formula (4) Polyimide precursor A body is exemplified. A practical upper limit is 100 mol % or less.

The weight average molecular weight (Mw) of the polyimide or polyamideimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. . Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.

Polyimide or polyamideimide preferably has a molecular weight distribution of 1.5 to 3.5, more preferably 2 to 3.

Polyimide or polyamideimide can be obtained, for example, by cyclizing a polyimide precursor or polyamideimide precursor, which is another resin described later, by heating or the like.

[Polyimide precursor, polyamideimide precursor (other resin)]
From the viewpoint of the film strength of the resulting cured film, the polyimide precursor or polyamideimide precursor preferably has a repeating unit represented by the above formula (1).

In the polyimide precursor or polyamideimide precursor, the number of repeating units represented by formula (1) may be one, or two or more. It may also contain structural isomers of the repeating unit represented by formula (1). The polyimide precursor or polyamideimide precursor may also contain other types of repeating units in addition to the repeating units of formula (1) above.
For example, the polyamideimide precursor preferably further contains a repeating unit containing an amide structure, or a repeating unit containing an amide structure and a carboxylic acid ester structure.

As one embodiment of the polyimide precursor or polyamideimide precursor in the present invention, 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units are repeating units represented by formula (1) is exemplified as a polyimide precursor. A practical upper limit is 100 mol % or less.

The weight average molecular weight (Mw) of the polyimide precursor or polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50. , 000. Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.

The polyimide precursor or polyamideimide precursor preferably has a molecular weight dispersity of 1.5 to 3.5, more preferably 2 to 3.

A polyimide precursor or polyamideimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.

In the method for producing a polyimide precursor or polyamideimide precursor, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.

Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

It is preferable that a step of precipitating a solid is included in the production of the polyimide precursor or the polyamideimide precursor. Specifically, the polyimide precursor or polyamideimide precursor in the reaction solution is precipitated in water and dissolved in a solvent in which the polyimide precursor or polyamideimide precursor is soluble, such as tetrahydrofuran, thereby causing solid precipitation. can be done.

When the curable resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more with respect to the total solid content of the curable resin composition. 05% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and 10% by mass or more. It is even more preferred to have
Further, the content of other resins in the curable resin composition of the present invention is preferably 80% by mass or less, and preferably 75% by mass or less, relative to the total solid content of the curable resin composition. More preferably, it is 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the curable resin composition of the present invention, the content of other resins may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, relative to the total solid content of the curable resin composition. It is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The curable resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Polymerization initiator>
The curable resin composition of the present invention preferably contains a polymerization initiator.
A photopolymerization initiator is preferable as the polymerization initiator.

[Photopolymerization initiator]
The curable resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.

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

As the radical photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. mentioned. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein.

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

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

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

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

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

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

Examples of metallocene compounds include IRGACURE-784 (manufactured by BASF).

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

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

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. An oxime-based photopolymerization initiator has a >C=N--O--C(=O)-- linking group in the molecule.

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

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

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

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

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

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

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

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

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

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

[Thermal polymerization initiator]
The curable resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator, as a polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can be advanced in the heating step described later, so that the chemical resistance can be further improved.

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

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

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

The number of radically polymerizable groups possessed by the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and may have three or more radically polymerizable groups. more preferred. The upper limit is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less.
On the other hand, from the viewpoint of developability, the radically polymerizable compound is particularly preferably a compound having two ethylenically unsaturated bonds.

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

From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least one difunctional or higher radically polymerizable compound containing two or more radically polymerizable groups, and a trifunctional or higher radically polymerizable compound. It is more preferable to include at least one of It may also be a mixture of a difunctional radically polymerizable compound and a trifunctional or higher radically polymerizable compound. For example, the number of functional groups of a polymerizable monomer having two or more functions means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably They are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and a polyvalent amine compound. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

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

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

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

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

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

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

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

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

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

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

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

The curable resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, 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 of bisphenol A Diacrylate, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimetharylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, An isocyanuric acid-modified dimethacrylate, a bifunctional acrylate having a urethane bond, and a bifunctional methacrylate having a urethane bond can be used. These can be used in combination of two or more as needed.
In the curable resin composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with elastic modulus control of the cured film. Monofunctional radically polymerizable compounds include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl ( (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radically polymerizable compound, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
In addition, the curable resin composition of the present invention can also contain allyl compounds such as diallyl phthalate and triallyl trimellitate as bifunctional or higher radically polymerizable compounds.

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

<Acid Generator>
The curable resin composition of the present invention preferably contains an acid generator.
As the acid generator, a photoacid generator is preferred.

[Photoacid generator]
The curable resin composition of the present invention preferably contains a photoacid generator.
By containing a photoacid generator, for example, acid is generated in the exposed portion of the curable resin composition layer, the solubility of the exposed portion in the developer (e.g., alkaline aqueous solution) is increased, and the exposed portion is A positive relief pattern can be obtained which is removed by the developer.
Further, when the curable resin composition contains a photoacid generator and an acid cross-linking agent described later, for example, the acid generated in the exposed area promotes the cross-linking reaction of the thermal cross-linking agent, and the exposed area becomes non-exposed. It is also possible to adopt a mode in which it is more difficult to remove with a developer than the exposed portion. According to such an aspect, a negative relief pattern can be obtained.

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

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

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

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

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

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

[Thermal acid generator]
The curable resin composition of the present invention may contain a thermal acid generator.
The thermal acid generator generates an acid upon heating and is at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound, or a specific resin. has the effect of promoting the cross-linking reaction of the methylol group contained in.
Moreover, when the curable resin composition of the present invention contains a thermal acid generator, the specific resin preferably contains an epoxy group or a methylol group as a polymerizable group.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, no acid is generated during drying (prebaking: about 70 to 140 ° C.) after applying the curable resin composition to the substrate, and the final heating (curing: about 100 to 400) after patterning by subsequent exposure and development. °C), it is preferable to select a thermal acid generator that generates an acid when the thermal acid generator is used, because it is possible to suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated up to 500° C. in a pressure-resistant capsule at 5° C./min.
Equipment used for measuring the thermal decomposition initiation temperature includes Q2000 (manufactured by TA Instruments).

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

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

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

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of the electrical insulation properties of the cured film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Acid crosslinking agent>
The photocurable resin composition of the present invention preferably contains an acid crosslinking agent.
In the present invention, the acid cross-linking agent is preferably a compound having a plurality of groups in the molecule that promote cross-linking reaction by the action of acid.
As the acid cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is attached to a nitrogen atom. Compounds with directly linked structures are more preferred.
Examples of acid cross-linking agents include reaction of amino group-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine with formaldehyde or formaldehyde and alcohol, and substituting a hydrogen atom of the amino group with a methylol group or an alkoxymethyl group. A compound having a structure represented by The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the amino group-containing compound, a melamine-based crosslinking agent is a melamine-based crosslinking agent, a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent, and an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent. A cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the photocurable resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of melamine-based cross-linking agents, and more preferably includes a glycoluril-based cross-linking agent.

Specific examples of melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycoluril. , trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, di propoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril, etc. a glycoluril-based cross-linking agent;
urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based cross-linking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxymethyl ethylene urea;
monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy propylene urea-based cross-linking agents such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like.

Specific examples of benzoguanamine cross-linking agents include monohydroxymethylated benzoguanamine and dihydroxymethylated benzoguanamine. trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine,
tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethyl benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.

Other compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups include at least one group selected from the group consisting of methylol groups and alkoxymethyl groups on an aromatic ring (preferably a benzene ring). Compounds in which groups are directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 ,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3′,5,5′-tetrakis ( methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.

Commercially available products may be used as the acid cross-linking agent, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML- BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Kogyo Co., Ltd.), Nikalac (registered trademark, hereinafter the same) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) etc.

The curable resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as an acid crosslinking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the curable resin composition.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740, Ricaresin (registered trademark) BEO-20E (the above products name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade names, manufactured by ADEKA Corporation), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 Serbinase B0134, B0177 (trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH- 75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like.

[Oxetane compound (compound having an oxetanyl group)]
The oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used. Or you may mix 2 or more types.

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

Preferable examples of benzoxazine compounds include Ba type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, Fa type benzoxazine (trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly Examples include benzoxazine adducts of hydroxystyrene resins and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of the acid crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Only one kind of acid cross-linking agent may be contained, or two or more kinds thereof may be contained. When two or more acid cross-linking agents are contained, the total is preferably within the above range.

<Compound having sulfonamide structure, compound having thiourea structure>
From the viewpoint of improving the adhesion of the resulting cured film to the substrate, the curable resin composition of the present invention contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure. It is preferable to further contain a compound of

[Compound having a sulfonamide structure]
A sulfonamide structure is a structure represented by the following formula (S-1).
In formula (S-1), R represents a hydrogen atom or an organic group, R may be combined with another structure to form a ring structure, * each independently represents a bonding site with another structure represent.
R above is preferably the same group as R ² in formula (S-2) below.
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

The compound having a sulfonamide structure is preferably a compound represented by formula (S-2) below.
In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ are A ring structure may be formed.
R ¹ , R ² and R ³ are each independently preferably a monovalent organic group.
Examples of R ¹ , R ² and R ³ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, A carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these can be mentioned.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , a pyrazine ring, a piperidine ring, a piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazine ring.

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

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1 -sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethyl methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide and the like.

[Compound having a thiourea structure]
A thiourea structure is a structure represented by the following formula (T-1).
In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ may combine to form a ring structure, and R ⁴ is * may be combined with another structure to which * is bonded to form a ring structure, R ⁵ may be combined with another structure to which * is bonded to form a ring structure, * is each independently represents the binding site with the structure of

Each of R ⁴ and R ⁵ is preferably independently a hydrogen atom.
Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, Examples include an allyl group, a vinyl group, a heterocyclic group, or groups in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , a pyrazine ring, a piperidine ring, a piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazine ring.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

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

In formula (T-2), R ⁴ and R ⁵ have the same definitions as R ⁴ and R ⁵ in formula (T-1), and preferred embodiments are also the same.
In formula (T-2), R ⁶ and R ⁷ are each independently preferably a monovalent organic group.
Preferred embodiments of the monovalent organic groups for R ⁶ and R ⁷ in formula (T-2) are the same as preferred embodiments of the monovalent organic groups for R ⁴ and R ⁵ in formula (T-1). .

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

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure with respect to the total mass of the curable resin composition of the present invention is preferably 0.05 to 10 mass%, and 0.1 to 5 mass. %, more preferably 0.2 to 3% by mass.
The curable resin composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more thereof. When only one kind is included, the content of the compound is preferably within the above range, and when two or more kinds are included, the total amount thereof preferably falls within the above range.

<Onium salt>
The curable resin composition of the present invention preferably contains an onium salt.
In particular, when a polyimide precursor is included as another resin, the curable resin composition preferably includes an onium salt.
Although the type of onium salt is not particularly limited, ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts are preferred.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

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

The onium salt used in the present invention may be a thermal base generator.
A thermal base generator is a compound that generates a base upon heating, and includes, for example, acidic compounds that generate a base when heated to 40° C. or higher.

[Ammonium salt]
In the present invention, an ammonium salt means a salt of an ammonium cation and an anion.

-Ammonium cation-
Preferred ammonium cations are quaternary ammonium cations.
Moreover, as the ammonium cation, a cation represented by the following formula (101) is preferable.
In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may combine to form a ring.

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

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

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

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

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

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

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

In the present invention, the carboxylate anion is preferably represented by the following formula (XA).
In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, —NR ^X — and combinations thereof, and R ^X is , represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt as an anion, from the viewpoint of facilitating the cyclization of the specific resin at low temperatures and facilitating the improvement of the storage stability of the curable resin composition. , preferably contains an anion whose pKa (pKaH) of the conjugate acid is 2.5 or less, more preferably 1.8 or less.
The lower limit of the pKa is not particularly limited, but from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific resin is improved, it is preferably -3 or more, and -2 or more. is more preferred.
Determination of Organic Structures by Physical Methods (Author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; Compilation: Braude, E.A.). ， Nachod, F. C.; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). can be done. For compounds not described in these documents, values calculated from structural formulas using software ACD/pKa (manufactured by ACD/Labs) are used.

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

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

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

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

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

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

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

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
Moreover, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

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

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

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

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. is more preferably an aryl group, more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

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

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. is more preferably an aryl group, more preferably a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

<Thermal base generator>
The curable resin composition of the present invention may contain a thermal base generator.
In particular, when the curable resin composition contains a polyimide precursor as another resin, the curable resin composition preferably contains a thermal base generator.
The thermal base generator may be a compound corresponding to the onium salt described above, or may be a thermal base generator other than the onium salt described above.
Other thermal base generators include nonionic thermal base generators.
Nonionic thermal base generators include compounds represented by formula (B1) or formula (B2).

In Formula (B1) and Formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

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

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

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

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

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

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

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

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

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

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

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of other thermal base generators include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

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

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

Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.

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

Specific examples of migration inhibitors include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and 0 It is more preferably from 0.05 to 2.0% by mass, and even more preferably from 0.1 to 1.0% by mass.

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

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

Examples of polymerization inhibitors include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone. , 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N- Nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl -4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy -2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl free radicals, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxyl Amine ammonium salts and the like are preferably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

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

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor, relative to the total solid content of the curable resin composition of the present invention, for example 0.01 to 20.0 mass% The content is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, even more preferably 0.05 to 2.5% by mass. In addition, when storage stability of the composition is required, an aspect of 0.02 to 15.0% by mass is also preferable, and in that case, 0.05 to 10.0% by mass is more preferable.

One type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

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

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

Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 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- Examples include isocyanatopropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used singly or in combination of two or more.

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

[Aluminum Adhesion Aid]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

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

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The electronically excited sensitizer comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes electron transfer, energy transfer, heat generation, and the like. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
Examples of sensitizers include sensitizers such as N-phenyldiethanolamine. In addition, benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, Compounds such as cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds can be used.
For example, 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-dimethylaminocinnamylideneindanone, p- dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3 -bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino ) coumarin-3-carboxylate ethyl), N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3′,4′-dimethylacetanilide and the like mentioned.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.

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

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. Chain transfer agents include, for example, a group of compounds having —S—S—, —SO ₂ —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of WO 2015/199219.

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. It is preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.

[Surfactant]
Various types of surfactants may be added to the curable resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various kinds of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parenthesis indicating the repeating unit of the main chain indicates the content (mol %) of each repeating unit, and the parenthesis indicating the repeating unit of the side chain indicates the repeating number of each repeating unit.
In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

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

[Higher Fatty Acid Derivative]
In the curable resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. It may be unevenly distributed on the surface of the object.

Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 2015/199219.

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. is preferred. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of coated surface properties.

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

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

Considering the use as a semiconductor material, the curable resin composition of the present invention has a halogen atom content of preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, more preferably less than 300 ppm by mass, from the viewpoint of wiring corrosion resistance. Less than ppm is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.

Conventionally known containers can be used as the container for the curable resin composition of the present invention. In addition, for the storage container, for the purpose of suppressing the contamination of the raw material and the curable resin composition, a multi-layer bottle whose inner wall is made of 6 types and 6 layers of resin, and 7 types of 6 types of resin are used. It is also preferred to use a layered bottle. Examples of such a container include the container described in JP-A-2015-123351.

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

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the curable resin composition. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When performing filtration by pressurization, the pressure to be applied is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , more preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

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

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, cured films, laminates, semiconductor devices, and manufacturing methods thereof will be described.

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

Two or more layers of the cured film of the present invention, or three to seven layers may be laminated to form a laminate. The laminate of the present invention preferably has two or more cured films and a metal layer between the cured films. Moreover, it is preferable that the laminate of the present invention includes two or more cured films and a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferred. Both the first cured film and the second cured film are cured films of the present invention, for example, both the first cured film and the second cured film have the curability of the present invention A preferred embodiment is a film obtained by curing a resin composition. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. They may be different compositions, but from the viewpoint of production suitability, they are preferably compositions with the same composition. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

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

The cured films according to the invention can also be used in the production of printing plates such as offset or screen printing plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. is preferred.
Furthermore, the method for producing a cured film of the present invention includes the film forming step, and further includes an exposure step of exposing the film and a developing step of developing the film (developing the film). is more preferable.
Furthermore, the method for producing a cured film of the present invention includes the film forming step (and the developing step if necessary), and further includes a heating step of heating the film at 50 to 450 ° C. preferable.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film forming step of applying a curable resin composition to a substrate to form a film (a curable resin composition layer); (b) an exposure step of exposing the film after the film forming step; A developing step (d) in which the developed film is subjected to development treatment (d) A heating step in which the developed film is heated at 50 to 450 ° C. By heating in the heating step, the curable resin composition layer after development is further increased. Can be cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed and sufficient curability is obtained.

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

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

The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate and a mold resin substrate are more preferable.
As the base material, for example, a plate-like base material (substrate) is used.

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

Coating is preferable as a means for applying the curable resin composition to the substrate.

Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the curable resin composition layer, the spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of the spin coating method, for example, at a rotation speed of 300 to 3,500 rpm, it may be applied for 10 to 180 seconds, and at a rotation speed of 500 to 2,000 rpm (revolutions per minute), 10 seconds to 1 minute. can be applied to some extent. Moreover, in order to obtain uniformity of the film thickness, it is also possible to apply by combining a plurality of number of revolutions.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after forming the film (curable resin composition layer) and after the film forming step (layer forming step). The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 3 minutes to 7 minutes. Vacuum drying and heat drying can be combined when the composition has a large amount of solvent. A hot plate, a hot air oven, or the like is used for drying by heating, and is not particularly limited.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly defined as long as the curable resin composition can be cured ^. It is more preferable to irradiate cm ² .

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

In relation to the light source, the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer Laser (wavelength: 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser with second harmonic of 532 nm and third harmonic of 355 nm. For the curable resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h and i lines) light source of a high pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

<Development process>
The production method of the present invention may include a development step of developing the exposed film (curable resin composition layer). By developing, for example, in the case of a negative photosensitive resin composition, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed.

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

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

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

Organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons such as toluene, xylene, anisole, etc. Group hydrocarbons, cyclic terpenes such as limonene, and sulfoxides include dimethyl sulfoxide.

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

Further, the developer may contain a surfactant.

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

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

After processing with the developer, rinsing may be carried out.
In the case of solvent development, rinsing is preferably performed using an organic solvent different from the developer. Examples include propylene glycol monomethyl ether acetate. Rinsing time is preferably 5 seconds to 5 minutes. A step of applying both a developer and a rinse may also be included between development and rinsing. The time for the above steps is preferably 1 second to 5 minutes.
In the case of alkali development, rinsing is preferably performed using pure water.
Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
The curable resin composition of the present invention contains a polymerizable compound other than the specific resin, and the curing reaction of the unreacted polymerizable compound other than the specific resin, the curing reaction of the unreacted polymerizable group in the specific resin, etc. can proceed with
Further, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal base generator, in the heating step, for example, a base is generated by decomposition of the thermal base generator, and the polyimide precursor A cyclization reaction proceeds.
The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, even more preferably 140° C. or higher, and 150° C. or higher. is particularly preferred, 160° C. or higher is more preferred, and 170° C. or higher is most preferred. The upper limit is preferably 450° C. or lower, more preferably 350° C. or lower, even more preferably 250° C. or lower, and particularly preferably 220° C. or lower.

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

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

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

Particularly when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason for this is not clear, it is thought that by setting the temperature at this temperature, the cross-linking reaction between the polymerizable groups in the specific resin between the layers proceeds.

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

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

The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or in a vacuum, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

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

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

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

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

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

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

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

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

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

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after providing the metal layer. Specifically, (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in this order, or (a) film formation (b) the exposure step, (c) the development step, and (e) the metal layer formation step, and the step (d) is collectively provided at the end or in the middle. By alternately performing the lamination step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

The invention also discloses a semiconductor device comprising the cured film or laminate of the invention. Specific examples of semiconductor devices using the curable resin composition of the present invention for forming an interlayer insulating film for rewiring layers are described in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. , the contents of which are incorporated herein.

(resin)
The resin of the invention preferably has a repeating unit represented by the following formula (1-1).
In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. group, n represents an integer of 1 or more, and ^Q1 represents a divalent linking group.

The above formula (1-1) has the same meaning as the formula (1-1) in the specific resin, and preferred embodiments are also the same.
The resin of the present invention has the same meaning as the specific resin described above, and preferred embodiments are also the same.

<Application>
The resin of the present invention is preferably used as a resin contained in a curable resin composition.
Moreover, in compositions using conventional polyimides, such as compositions for interlayer insulating films, the resin of the present invention can be used without particular limitation by replacing part or all of the conventional polyimides.
Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is, for example, a composition for forming an insulating film, a composition for forming a laminate, etc. Chemical resistance is required. It is considered to be suitable for use in compositions used for purposes.

(Resin manufacturing method)
The method for producing the resin of the present invention is a method for producing the resin of the present invention, wherein a compound A having at least two hydroxy groups and at least one reactive group forms a bond with the reactive group. and a compound B having a polymerizable group to obtain a diol compound (diol production step), the diol compound and a compound having three carboxy groups, or the three carboxy groups A step of obtaining a tetravalent carboxylic acid compound having two ester bonds (a tetravalent carboxylic acid compound manufacturing step), and reacting the tetravalent carboxylic acid compound with a diamine compound It is preferable to include a step of obtaining a polyimide precursor (precursor manufacturing step) and a step of imidizing the polyimide precursor (imidation step).
The details of each of the above steps are as described in the method for producing the specific resin, and the preferred embodiments are also the same.

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

(Synthesis of specific resin)
<Synthesis of Intermediate AA>
In a flask equipped with a condenser and stirrer, 48.5 g (0.4 mol) of 2-amino-2-(hydroxymethyl)-1.3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 240 mL of acetone. and cooled to 0° C., 39.2 g (0.41 mol) of methanesulfonic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. Then, 62.5 g (0.6 mol) of 2,2-dimethoxypropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring at 25° C. for 3 hours. The precipitate was filtered, washed with 500 mL of acetone, and filtered. This was vacuum dried to obtain 99.0 g of intermediate (AA). It was confirmed from the NMR spectrum that it was the intermediate (AA). Intermediate (AA) was analyzed by ¹ H-NMR. The results are shown below.
¹ H-NMR data (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.39 (s, 6H), 2.31 (s, 3H), 3.48-3.50 (d, 2H), 3.64-3.67 (d, 2H), 3 .88-3.91 (d, 2H), 5.46-5.49 (t, 1H), 8.03 (s, 3H)

<Synthesis of Intermediate AB>
In a flask equipped with a condenser and stirrer, 38.6 g (0.15 mol) of intermediate (AA) and 54.6 g (0.54 mol) of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) , 167 g of tetrahydrofuran and cooled to 0°C. Then, 32.9 g (0.315 mol) of methacrylic acid chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour, followed by stirring at 0°C for 1 hour and at 25°C for 2 hours. The reaction was then transferred to a separatory funnel, diluted with 700 mL of ethyl acetate, washed with 300 mL of water, washed twice with 300 mL of saturated aqueous ammonium chloride, washed with 300 mL of water, and washed with saturated brine. did. This was dried over magnesium sulfate, concentrated by an evaporator, and column-purified using a solvent of ethyl acetate/hexane=20/80 (mass ratio). This was concentrated to obtain 20.0 g of intermediate (AB). It was confirmed from the NMR spectrum that it was the intermediate (AB). Intermediate (AB) was analyzed by ¹ H-NMR. The results are shown below.
¹ H-NMR data (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.32 (s, 3H), 1.38 (s, 3H), 1.81 (s, 3H), 1.88 (s, 3H), 3.90-3.93 (d , 2H), 4.03-4.06 (d, 2H), 4.44 (s, 2H), 5.34 (s, 1H), 5.60 (s, 1H), 5.69 (s, 1H), 7.51 (s, 1H)

<Synthesis of intermediates AC>
In an eggplant flask, 13.4 g (0.45 mol) of intermediate (AB) was dissolved in 150 mL of acetonitrile, 4.0 g of water, acidic resin DOWEX (50 W × 40 200-400 Mesh) (Aldrich Co., Ltd.) (manufactured by Co., Ltd.) was added, and the mixture was stirred at 30°C for 6 hours. 20.0 g of magnesium sulfate was added thereto, and the mixture was stirred for 10 minutes, filtered through filter paper, and concentrated by an evaporator to obtain 10.5 g of intermediate (AC). It was confirmed from the NMR spectrum that it was the intermediate (AC). Intermediate (AC) was analyzed by ¹ H-NMR. The results are shown below.
¹ H-NMR data (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.83 (s, 3H), 1.87 (s, 3H), 3.64-3.66 (d, 4H), 4.33 (s, 2H), 4.89-4 .92 (t, 2H), 5.33 (s, 1H), 5.58 (s, 1H), 5.66 (s, 1H), 6.03 (s, 1H), 6.99 (s, 1H)

<Synthesis of anhydrides (AA-1 to AA-7)>
In a flask equipped with a condenser and a stirrer, 18.5 g (0.88 mol) of trimellitic anhydride chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.8 g of ethyl acetate and cooled to -10°C or below. did. Then, 10.2 g (0.04 mol) of intermediate (AC) and 7.12 g (0.09 mol) of pyridine were dissolved in 34.6 g of ethyl acetate and added dropwise over 1 hour. After dropping, the mixture was stirred at −10° C. or below for 1 hour and at 25° C. for 2 hours. Then, the reaction solution was transferred to a separating funnel while being filtered through filter paper, diluted with 700 mL of ethyl acetate, washed with 300 mL of water, washed twice with 200 mL of saturated aqueous sodium bicarbonate solution, washed with 200 mL of aqueous hydrochloric acid solution and saturated saline solution. washed with This was dried over magnesium sulfate and concentrated by an evaporator, and the ethyl acetate solution was crystallized in hexane. This was filtered and vacuum dried to obtain 21.0 g of anhydride (AA-1). It was confirmed from the NMR spectrum that it was an anhydride (AA-1). The anhydride (AA-1) was analyzed by ¹ H-NMR. The results are shown below.
¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.95-1.96 (d, 6H), 4.72 (s, 2H), 4.96-5.02 (q, 4H), 5.45 (s, 1H), 5 .67 (s, 1H), 5.74 (s, 1H), 6.16 (s, 1H), 6.72 (s, 1H), 8.13-8.15 (d, 2H), 8. 55-8.59 (m, 4H)
Anhydrides (AA-2) to (AA-8) having the following structures were synthesized in the same manner.

<Synthesis of polyester polyimide resin (PA-1)>
In a flask equipped with a condenser and stirrer, 15.1 g (25 mmol) of anhydride (AA-1), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then 4.91 g (24.5 mmol) of 4,4'-diaminodiphenyl ether was added and stirred at 25°C for 3 hours and at 80°C for a further 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to cause precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-1). The molecular weight of PA-1 was Mw=82,100 and Mn=32,500.
The structure of PA-1 is presumed to be a structure represented by the following formula (PA-1).

<Synthesis of polyester polyimide resin (PA-2)>
In a flask equipped with a condenser and stirrer, 14.4 g (25 mmol) of anhydride (AA-2), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 4.91 g of 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.85 g (24.5 mmol) of biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 25° C. for 3 hours. Stir and stir at 80° C. for an additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-2). The molecular weight of PA-2 was Mw=65,500 and Mn=28,300.
The structure of PA-2 is presumed to be a structure represented by the following formula (PA-2).

<Synthesis of polyester polyimide resin (PA-3)>
In a flask equipped with a condenser and stirrer, 19.4 g (25 mmol) of anhydride (AA-4), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.85 g (24.5 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25°C for 3 hours, Stir at 80° C. for an additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to cause precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-3). The molecular weights of PA-3 were Mw=88,500 and Mn=36,300.
The structure of PA-3 is presumed to be a structure represented by the following formula (PA-3).

<Synthesis of polyester polyimide resin (PA-4)>
In a flask equipped with a condenser and stirrer, 17.9 g (25 mmol) of anhydride (AA-5), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.85 g (24.5 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25°C for 3 hours, Stir at 80° C. for an additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-4). The molecular weight of PA-4 was Mw=88,500 and Mn=36,300.
The structure of PA-4 is presumed to be a structure represented by the following formula (PA-4).

<Synthesis of polyester polyimide resin (PA-9)>
In a flask equipped with a condenser and stirrer, 15.1 g (25 mmol) of anhydride (AA-1), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 6.87 g (24 mmol) of bis(4-amino-3-carboxyphenyl)methane (manufactured by Wakayama Seika Co., Ltd.) was added, stirred at 25°C for 3 hours, and stirred at 80°C for additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-9). The molecular weight of PA-9 was Mw=38,200 and Mn=16,400.
The structure of PA-9 is presumed to be the structure represented by the following formula (PA-9).

<Synthesis of polyester polyimide resin (PA-10)>
12.44 g (17.5 mmol) of anhydride (AA-6), 3.77 g (7.5 mmol) of anhydride (AA-7) while removing water in a flask equipped with a condenser and stirrer. , 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 6.87 g (24 mmol) of bis(4-amino-3-carboxyphenyl)methane (manufactured by Wakayama Seika Co., Ltd.) was added, stirred at 25°C for 3 hours, and stirred at 80°C for additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-10). The molecular weight of PA-10 was Mw=32,400 and Mn=15,200.
The structure of PA-10 is presumed to be a structure having two repeating units represented by the following formula (PA-10). In the following structural formulas, subscripts in parentheses indicating repeating units represent the content ratio (molar ratio) of each repeating unit.

<Synthesis of polyester polyimide resin (PA-11)>
In a flask equipped with a condenser and stirrer, 15.4 g (25 mmol) of anhydride (AA-8), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 8.71 g (25 mmol) of 4,4'-(9-fluorenylidene)dianiline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, stirred at 25°C for 3 hours, and stirred at 80°C for additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain a polyester polyimide resin (PA-11). The molecular weight of PA-11 was Mw=55,600 and Mn=22,700.
The structure of PA-11 is presumed to be a structure represented by the following formula (PA-11).

<Synthesis of polyester polyimide resin (PA-12)>
6.28 g (12.5 mmol) of anhydride (AA-7), 6.53 g (12.5 mmol) of anhydride (AA-3) while removing water in a flask equipped with a condenser and stirrer. , 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 4,90 g (24.5 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, stirred at 25°C for 3 hours, and stirred at 80°C for additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to cause precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for 1 day. Next, the dried resin is dissolved in 70.0 g of N-methylpyrrolidone (NMP), and 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) is added. and cooled to 0°C. Then, 1.58 g (12.5 millimoles) of diisopropylcarbodiimide and 1.11 g (15 millimoles) of glycidol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added, stirred at 10°C or less for 5 hours, and heated to room temperature. Then, it was cooled to 25° C., precipitated in 1.5 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 3,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, spray-washed with 1 liter of water, mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. After drying for days, a polyester polyimide resin (PA-12) was obtained. The molecular weight of PA-12 was Mw=57,400 and Mn=24,800.
The structure of PA-12 is presumed to be a structure containing two repeating units represented by the following formula (PA-12). In formula (PA-12), * represents a binding site with the oxygen atom to which _R1 binds.

<Synthesis of polyimide precursor (PI-1)>
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of Hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme are mixed and stirred at a temperature of 60° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. did. The reaction mixture was then cooled to -10.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. Viscosity increased during SOCl ₂ addition. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was then added to the reaction mixture over 20 minutes while maintaining the temperature between -5 and 0°C. Dripped. Then, the solution and the reaction mixture were allowed to react at 0° C. for 1 hour, then 70 g of ethanol was added, and the mixture was stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45° C. for 3 days to obtain a polyimide precursor (PI-1). The weight average molecular weight of this polyimide precursor (PI-1) was 22,000.
The structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).

<Synthesis of comparative polyimide (A-1)>
20.0 g (100 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) while removing water in a dry reactor equipped with a stirrer, condenser and a flat-bottomed joint fitted with an internal thermometer. was dissolved in 200.0 g of N-methylpyrrolidone (NMP). Subsequently, 44.4 g (100 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added and stirred at a temperature of 40° C. for 2 hours. Then, after adding 50 mL of toluene, the temperature was raised to 180° C. while flowing nitrogen at a flow rate of 200 ml/min, stirred for 9 hours, and cooled to room temperature. Then, 130.0 g of N-methylpyrrolidone was added and after dilution, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was obtained by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was then dried under reduced pressure at 40° C. for 1 day to obtain a comparative polyimide (A-1). A-1 had a weight average molecular weight (Mw) of 78,200 and a number average molecular weight (Mn) of 30,500.
Comparative polyimide (A-1) does not contain a repeating unit represented by formula (1-1) and does not correspond to a specific resin.
The structure of A-1 is presumed to be a structure represented by the following formula (A-1).

<Synthesis of comparative polyimide (A-2)>
In a flask equipped with a condenser and a stirrer, while removing water, 11.5 g (25 mmol) of an anhydride (a-1) having the structure represented by the following formula (a-1), 2,2,6 , 6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Then, 4.91 g of 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.85 g (24.5 mmol) of biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 25° C. for 3 hours. Stir and stir at 80° C. for an additional 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) are added and stirred at 80° C. for 3 hours to obtain N-methylpyrrolidone. (NMP) 50 g was added and diluted.
The reaction solution was added to 1.5 liters of methanol to induce precipitation and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for 1 day to obtain a comparative polyimide (A-2). The molecular weights of A-2 were Mw=85,100 and Mn=36,900.
Comparative polyimide (A-2) does not contain the repeating unit represented by formula (1-1) and does not correspond to a specific resin.
The structure of A-2 is presumed to be a structure represented by the following formula (A-2).

<Examples and Comparative Examples>
In each example, the components shown in Table 1 below were mixed to obtain each curable resin composition. In addition, in each comparative example, the components shown in Table 1 below were mixed to obtain each comparative composition. The resulting curable resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In Table 1, the numerical values in the "parts by mass" column indicate the content (parts by mass) of each component.
In Table 1, for example, "PA-1/PI-1" in the "type" column, "18/14" in the "parts by mass" column, etc. are 18 parts by mass of PA-1, PI-1 14 parts by mass of each was used.
In addition, in Table 1, the description of "-" indicates that the corresponding component is not contained.

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

[Specific resin or comparative resin]
- PA-1 to PA-11: PA-1 to PA-11 synthesized above
- PI-1: PI-1 synthesized above
· A-1 to A-2: A-1 to A-2 synthesized above

〔solvent〕
・DMSO: dimethyl sulfoxide ・GBL: γ-butyrolactone ・EL: ethyl lactate ・NMP: N-methylpyrrolidone It shows that they were used by mixing at a ratio.
In Table 1, the description of NMP/EL indicates that NMP and ethyl lactate were mixed at a ratio of NMP:ethyl lactate=80:20 (mass ratio).

[Polymerization initiator or acid generator]
・OXE-01: IRGACURE OXE 01 (manufactured by BASF)
・OXE-02: IRGACURE OXE 02 (manufactured by BASF)
・ DFY: diphenyliodonium trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ NQD: sodium 1,2-naphthoquinone-2-diazide-5-sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Polymerizable compound or acid cross-linking agent]
・ SR-209: SR-209 (manufactured by Sartomer)
・ SR-231: SR-231 (manufactured by Sartomer)
・ SR-239: SR-239 (manufactured by Sartomer)
・ ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ TMGU: 1.3.4.6-tetrakis (methoxymethyl) glycoluril (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ICATG: triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Polymerization inhibitor]
・F-1: 1,4-benzoquinone ・F-2: 4-methoxyphenol ・F-3: 1,4-dihydroxybenzene ・F-4: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd. ) made)

[Metal adhesion improver]
- G-1 to G-4: compounds having the following structures. In the structural formulas below, Et represents an ethyl group.

[Migration inhibitor]
・H-1: 1H-tetrazole ・H-2: 1,2,4-triazole ・H-3: 5-phenyltetrazole

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

〔Additive〕
・ J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation>
[Developer solubility evaluation]
Developer solubility evaluation was carried out as follows.
Each curable resin composition or comparative composition prepared in each example and comparative example was applied onto a silicon wafer by spin coating to form a curable resin composition layer.
The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform curable resin composition layer with a thickness of 35 μm on the silicon wafer.
The curable resin composition layer on the silicon wafer was exposed to i-rays with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposure was performed using a binary mask having a 1:1 line-and-space pattern with a width of 50 μm, 70 μm, or 100 μm.
For the curable resin composition layer after exposure, in the example described as "solvent" in the column "developing method (developer)" in Table 1, for the curable resin composition layer after exposure Development was performed using cyclopentanone at 30° C. as a developer, and rinsing was performed with PGMEA (propylene glycol monomethyl ether acetate).
In the example described as "alkali" in the column of "developing method (developer)" in Table 1, 2.38% by mass of tetra tetraethylene at 30°C was used as the developer for the curable resin composition layer after exposure. Development was performed using a methylammonium hydroxide aqueous solution, and rinsing was performed using deionized water.
A 1:1 line and space (L/S) pattern with a width of 100 μm is used during exposure, and the minimum time required for dissolving the unexposed portion when the thickness of the curable resin composition layer is 35 μm is the minimum development time. and evaluated according to the following evaluation criteria. It can be said that the shorter the minimum development time, the better the developer solubility. The evaluation results are shown in Table 1.
-Evaluation criteria-
A: The above minimum development time was within 30 seconds.
B: The above minimum development time was over 30 seconds and within 60 seconds.
C: The above minimum development time was over 60 seconds and within 120 seconds.
D: Not completely dissolved in 120 seconds.

[Resolution evaluation]
In each example or comparative example, a silicon wafer having a curable resin composition layer was produced by the same method as the developer solubility evaluation, and a 1:1 line and space (L/ S) A patterned exposure was performed.
Development and rinsing were carried out in the same manner as in the developer solubility evaluation, except that the development time was twice the minimum development time in the developer solubility evaluation, and then dissolved. A portion where the surface of the silicon wafer was exposed was observed to confirm whether resolution was achieved.
Twenty-seven points of dissolved portions in the pattern of the cured film after development were measured and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
A: All 50 μm L/S patterns could be resolved.
B: At 50 μm, one or more were not resolved, and all 70 μm L/S patterns could be resolved. C: One or more of the 70 μm L/S patterns were not completely resolved, and all 100 μm An L/S pattern could be resolved.
D: One or more 100 μm L/S patterns were not completely resolved due to development residue or the like.

[Evaluation of chemical resistance]
Each curable resin composition or comparative composition prepared in each example and comparative example was applied onto a silicon wafer by spin coating to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the curable resin composition layer on the silicon wafer is exposed with an exposure energy of 500 mJ/cm ² , and the exposed curable resin composition layer (resin layer) is exposed to nitrogen. Under the atmosphere, the temperature is raised at a temperature increase rate of 10 ° C./min, and heated for 180 minutes at the temperature described in the "Curing conditions" column of Table 1 to form a cured layer (resin layer) of the curable resin composition layer. got
The obtained resin layer was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The resin layer was immersed in the chemical solution at 75 ° C. for 15 minutes, and the The film thicknesses were compared and the dissolution rate (nm/min) was calculated.
Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 1. It can be said that the lower the dissolution rate, the better the chemical resistance.
-Evaluation criteria-
A dissolution rate was less than 200 nm/min.
B The dissolution rate was 200 nm/min or more and less than 300 nm/min.
The dissolution rate of C was 300 nm/min or more and less than 400 nm/min.
D Dissolution rate was 400 nm/min or more.

From the above results, it can be seen that the curable resin composition containing the specific resin according to the present invention has excellent chemical resistance.
Comparative compositions according to Comparative Examples 1 to 3 do not contain specific resins. It can be seen that the comparative compositions according to Comparative Examples 1 to 3 are inferior in chemical resistance.

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

Claims (16)

including a resin having a repeating unit represented by the following formula (1-1) and a solvent,
A curable resin composition.

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. wherein the polymerizable group in A ¹ is a (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group, and n is 1 or more. and Q ¹ represents a divalent linking group. including a resin having a repeating unit represented by the following formula (1-1) and a solvent,
A curable resin composition.

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. A ¹ is an acryloxy group, a methacryloxy group, an acrylamide group, a group represented by the following formula (PL-1) or formula (PL-2), or a methoxymethyl group, and n is represents an integer of 1 or more, and Q ¹ represents a divalent linking group.

In formulas (PL-1) and (PL-2) above, * represents a binding site with ^Y1 . The curable resin composition according to claim 1 or 2, further comprising a radical photopolymerization initiator and a radically polymerizable compound. The polymerizable group in A ¹ in the formula (1-1) is a (meth)acrylamide group, (meth)acryloxy group, maleimide group, or vinylphenyl group, and a radical photopolymerization initiator and radical polymerization The curable resin composition according to claim 1, comprising a curable compound. 3. The curable resin composition according to claim 1, further comprising an acid generator and an acid cross-linking agent. 6. The structure according to any one of claims 1 to 5, wherein said Q ¹ comprises at least one structure selected from the group consisting of structures represented by formulas (A-1) to (A-5) below. curable resin composition.
In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 are each independently a hydrogen atom; , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, or a group containing a halogen atom , and L ^A31 and L ^A41 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group, * each independently represents a binding site to another structure . Q above ¹ The curable resin composition according to any one of claims 1 to 6, wherein contains an acid group. The curable resin composition according to any one of claims 1 to 7, wherein Y ¹ is an n+2 valent hydrocarbon group. The curable resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for rewiring layers. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 9. A laminate comprising two or more layers of the cured film according to claim 10 and having a metal layer between any of the cured films. A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of claims 1 to 9 to a substrate to form a film. The method for producing a cured film according to claim 12, comprising the step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 10 or the laminate according to claim 11. A resin having a repeating unit represented by the following formula (1-1).

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+2 valent organic group, and A ¹ contains a polymerizable group. wherein the polymerizable group in A ¹ is a (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group, and n is 1 or more. and Q ¹ represents a divalent linking group. A production method for producing the resin according to claim 15,
A compound A having at least two hydroxy groups and at least one reactive group is reacted with a compound B having a group capable of forming a bond with the reactive groups and a polymerizable group to produce a diol compound. the step of obtaining
A step of reacting the diol compound with a compound having three carboxy groups or a derivative of the compound having three carboxy groups to obtain a tetravalent carboxylic acid compound having two ester bonds;
A step of reacting the tetravalent carboxylic acid compound with a diamine compound to obtain a polyimide precursor, and
comprising imidizing the polyimide precursor,
The polymerizable group in the compound B is a (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group,
A method of manufacturing a resin.