WO2021045126A1

WO2021045126A1 - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, resin, and method for producing resin

Info

Publication number: WO2021045126A1
Application number: PCT/JP2020/033326
Authority: WO
Inventors: 敦靖野崎
Original assignee: 富士フイルム株式会社
Priority date: 2019-09-05
Filing date: 2020-09-02
Publication date: 2021-03-11
Also published as: TW202116876A; JP7254194B2; JPWO2021045126A1

Abstract

Provided are: a curable resin composition including a photosensitizer and a resin that includes repeating units represented by formula (1-1), the curable resin composition being such that the resin includes 50 mol% or more of repeating units represented by formula (1-1) relative to the total repeating units of the resin; a cured film obtained by curing the curable resin composition; a laminate including the cured film; a method for producing the cured film; a semiconductor device including the cured film or the laminate; a resin having repeating units represented by formula (1-1); and a method for producing the resin.

Description

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

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.

Resins such as polyimide are applied to various applications because they have excellent heat resistance and insulating properties. The above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, a resin such as polyimide may be used in the form of a curable resin composition containing a polyimide precursor or the like. The precursor is cyclized to become a resin such as polyimide by heating, for example.
Since these curable resin compositions can be applied to a base material or the like by a known coating method or the like, for example, there is a degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it is highly adaptable to manufacturing.
In addition to the high performance of resins such as polyimide, from the viewpoint of excellent manufacturing adaptability, curable resin compositions containing resins such as polyimide precursors are expected to be increasingly applied in industry. There is.

For example, Patent Document 1 describes a reactive transparent polyimide precursor having a specific structure.
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.

Special Table 2006-521452 Japanese Unexamined Patent Publication No. 2009-251451

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

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

Hereinafter, examples of typical embodiments of the present invention will be described.
<1> Contains a resin containing a repeating unit represented by the formula (1-1) and a photosensitizer.
The resin contains 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.
Curable resin composition;

In formula (1-1), X ¹ represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in ^{X 1 are aromatic hydrocarbons.} It is a hydrogen group, Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group, A ¹ represents a group containing a polymerizable group, and G ¹ and G ² are independent hydrogen atoms or substituents, respectively. Represents, and n represents an integer of 1 or more.
<2> The above-mentioned substituent containing an ethylenically unsaturated group with respect to the total molar amount of the ^{above-mentioned G 1} and the above-mentioned G ² in all the repeating units represented by the above-mentioned formula (1-1) contained in the above-mentioned resin. The curable resin composition according to <1>, wherein the ratio of the molar amount of G ¹ or the above G ^{2 is 0 to 30%.}
^{<3> With respect to the total molar amount of G 1} and G ² in all the repeating units represented by the above formula (1-1) contained in the resin, the number of carbon atoms which may contain a hetero atom is 1 to 30. The curable resin composition according to <1> or <2>, wherein the ratio of the molar amount of the organic group G ¹ or G ^{2 is 20 to 100%.}
<4> The G, which is an organic group having a polyalkyleneoxy group, with respect to the total molar amount of ^{G 1} and G ² in all the repeating units represented by the above formula (1-1) contained in the resin. The curable resin composition according to any one of <1> to <3>, wherein the ratio of the molar amount of ¹ or G ^{2 is 20 to 100%.}
<5> The above X ¹ includes at least one structure selected from the group consisting of the structures represented by the following formulas (A-1) to (A-5), and the above Y ¹ is the following formula. The curable resin according to any one of <1> to <4>, which comprises at least one structure selected from the group consisting of the structures represented by (A2-1) to (A2-5). Composition;

In formulas (A-1) to (A-5), ^RA11 to ^RA14 , ^RA21 to ^RA24 , ^RA31 to ^RA38 , ^RA41 to ^RA48 and ^RA51 to ^RA58 are independently hydrogen atoms. , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and ^LA31 and ^LA41 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene ^group, two of R A11 ^{~ R ^A14,} two of R A21 ^{~ R A24} , 2 of ^RA31 to ^RA38 , 2 of ^RA41 to ^RA48 , and 2 of ^RA51 to ^RA58 are binding sites with the carbonyl group in the above formula (1-1). Often, * represents the site of connection with other structures independently;

Wherein ^{(A2-1) ~ (A2-5),} R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and ^{^R} A251 ^~ ^R ^A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and ^LA231 and ^LA241 are independently single-bonded, carbonyl group, sulfonyl group and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene ^group, at least one of R A211 ^{~ R ^A214,} at least one of R a 221 ^{~ R A224} ^one, at least one of ^R A231 ^~ R ^{^A238,} at least one of R a 241 ^{~ R A248,} ^and, at least one of ^R A251 ^~ R ^A258 is between ^{a 1} in the formula (1-1) It may be a binding site, and each independently represents a binding site with another structure.
<6> The ^{curing according to any one of <1> to <5>, wherein A 1} contains a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group as the polymerizable group. Sex resin composition.
<7> The curable resin composition according to any one of <1> to <6>, wherein the photosensitizer is a photopolymerization initiator.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer.
<9> A cured film obtained by curing the curable resin composition according to any one of <1> to <8>.
<10> A laminate having two or more cured films according to <9> and having a metal layer between any of the cured films.
<11> A method for producing a cured film, which comprises 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>, which comprises a step of heating the film at 50 to 450 ° C.
<13> A semiconductor device having the cured film according to <9> or the laminate according to <10>.
<14> A resin containing 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the above resin.

In the formula (1-1), X ¹ represents a tetravalent group containing an aromatic hydrocarbon group, and the bonding sites with the four carbonyl groups in the formula (1-1) in ^{X 1 are all aromatic.} Group hydrocarbon groups, Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group, A ¹ represents a group containing a polymerizable group, and G ¹ and G ² are independent hydrogen atoms or groups. It represents a substituent and n represents an integer of 1 or more.
<15> The resin according to <14>, which has an acid value of 0 to 2.0 mmol / g.
<16> The method for producing a resin according to <14> or <15>.
A compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group is reacted with a group capable of forming a bond with the reactive group and a compound B having a polymerizable group. After the compound A and the compound B are bonded to each other to obtain a compound C, the nitro group in the compound C is reduced to obtain a diamine having an aromatic hydrocarbon group, and
Production of a resin including a step of reacting the diamine with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the tetravalent carboxylic acid compound. Method.

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

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present 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, the weight average molecular weight (Mw) and the 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, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement is assumed to use a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or, if there is a curable resin composition layer, the direction from the base material to the curable resin composition layer. Is called "upper", and the opposite direction is called "lower". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(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 containing a repeating unit represented by the following formula (1-1) and a photosensitizer. The resin contains 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.
Hereinafter, a resin containing 50 mol% or more of the repeating unit represented by the formula (1-1) with respect to all the repeating units of the resin is also referred to as a “specific resin”.

In formula (1-1), X ¹ represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in ^{X 1 are aromatic hydrocarbons.} It is a hydrogen group, Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group, A ¹ represents a group containing a polymerizable group, and G ¹ and G ² are independent hydrogen atoms or substituents, respectively. Represents, and n represents an integer of 1 or more.

The curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition, but is preferably a negative type curable resin composition. ..
The negative type curable resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.
The positive type curable resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.

The curable resin composition of the present invention is excellent in chemical resistance of the obtained cured film.
The mechanism by which the above effect is obtained is not clear, but it is presumed as follows.

The curable resin composition of the present invention contains a resin having a repeating unit represented by the above formula (1-1) (hereinafter, also referred to as “specific resin”).
Here, unlike the polyimide resin conventionally used, in the specific resin, the bonding sites with the four carbonyl groups in ^{X 1} ^{are all aromatic hydrocarbon groups, and Y 1} contains a polymerizable group. is a repeating unit having a group a ^1, comprising a repeating unit represented by the formula (1-1), 50 mol% or more based on all repeating units in the resin. Therefore, for example, as compared with the case where a conventionally used ^{polyimide having a polymerizable group at a position corresponding to G 1} or G ² in the formula (1-1) is used, the obtained cured film has a polymerizable group. The density of the crosslinked structure formed by the crosslinking (crosslinking density) increases. It is presumed that due to the increase in the crosslink density, a cured film having excellent chemical resistance can be obtained according to the curable resin composition of the present invention.
Further, by attachment to the four carbonyl groups in the X ¹ are both an aromatic hydrocarbon group, for reasons such as to improve the electrophilicity of the carbonyl group, when heated (especially, for example, of 180 ° C., such as It is considered that the ring closure rate at low temperature heating) is improved and the elongation at break (film strength) is improved.
Since the cured film has excellent chemical resistance, for example, another curable resin composition containing a solvent is further applied and cured on the cured film obtained by curing the curable resin composition of the present invention, and the laminated body is cured. It is considered that the dissolution of the cured film is suppressed even if the cured film comes into contact with the developing solution or other curable resin composition in the case of producing.
According to the present invention, for example, a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, or the polar solvent and the alkaline aqueous solution. It is considered that a cured film having excellent chemical resistance and whose solubility in the mixed solution of the above is suppressed can be obtained.
Further, the polyimide precursor is cyclized (imidized) by heating or the like and used as a resin such as polyimide. In the specific resin used in the present invention, the amount of the polymerizable group introduced at the position corresponding to ^{G 1} or G ² in the formula (1-1) is reduced, or the position corresponding to ^{G 1} or G ^{2 is reduced.} It is also possible to adopt a mode in which a polymerizable group is not introduced into the product. Therefore, it is presumed that the specific resin is easier to cyclize than the conventionally used polyimide resin, and the ring closure rate is improved. In addition, it is presumed that cyclization is likely to occur even when heated at a low temperature.
Further, for example, it is possible to design to introduce a group other than the polymerizable group (for example, a polyalkyleneoxy group) at the position corresponding to ^{the above G 1} or G ^2. With such a design, it is considered possible to increase the solvent solubility or the solubility in the developing solution while improving the ring closure rate as described above.
As described above, in the specific resin used in the present invention, there is also an advantage that the degree of freedom of design in ^{G 1} and G ² is widened by introducing ^{A 1} which is a group containing a polymerizable group into ^{Y 1.} To do.

Here, Patent Documents 1 and 2 do not describe or suggest a resin containing 50 mol% or more of the repeating unit represented by the formula (1-1) with respect to all the repeating units of the resin. Further, the curable resin composition in Patent Document 1 or 2 has a problem that the chemical resistance of the obtained cured film is low.

<Specific resin>
The curable resin composition of the present invention contains a specific resin.
The specific resin contains 50 mol% or more of the repeating units represented by the formula (1-1) with respect to all the repeating units of the specific resin.
The specific resin may have a repeating unit represented by the formula (1-1) in the side chain, but preferably has a repeating unit represented by the formula (1-1) in the main chain.
In the present specification, the "main chain" refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other binding chains.

[Repeating unit represented by equation (1-1)]
-X ^1-
In formula (1-1), X ¹ represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in ^{X 1 are aromatic hydrocarbons.} It is a hydrogen group.
In the formula (1-1), an aromatic hydrocarbon group for X ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms More preferably, it is a group obtained by removing four hydrogen atoms from the benzene ring or the naphthalene ring, and particularly preferably, it is a group obtained by removing four hydrogen atoms from the benzene ring.
The aromatic hydrocarbon group may have a substituent as long as the effect of the present invention can be obtained. Examples of the substituent include an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkyl halide group, a hydroxy group, a carboxy group, a sulfo group, a halogen atom and the like.
In the present invention, when simply describing "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl group", "alkylene group", etc., these groups have a branched structure and a cyclic structure unless otherwise specified. It may have at least one of the structures. For example, "alkyl group" includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination thereof, unless otherwise specified.

In the following formula (1-1 '), shows four coupling four carbonyl groups and ^{X 1} in formula (1-1), respectively as 1a ~ 4a.

In the formula (1 over ^{^{^{1 '), X 1, Y}}} 1, A 1, G 1, G 2, and n, ^X 1 in the formula ^{^{(1-1), Y 1, A}} 1, G 1, G 2 , And n.
"All the bonding sites with the four carbonyl groups in the formula (1-1) in ^{X 1} are aromatic hydrocarbon groups" means that the bonds represented by 1a to 4a are all included in ^{X 1.} It means that it is directly bonded to an aromatic hydrocarbon group.
Hereinafter, the bond represented by 1a is also referred to as "bond 1a" or the like.
Bonds 1a to 4a may each be bonded to the same aromatic hydrocarbon group among the aromatic hydrocarbon groups contained ^{in X 1, or may be bonded to different aromatic hydrocarbon groups.}
An aromatic in which bond 1a and bond 2a are bonded to the same aromatic hydrocarbon group, and bond 3a and bond 4a are the same aromatic hydrocarbon group, and bond 1a and bond 2a are bonded. It is preferable to bond to an aromatic hydrocarbon group different from the hydrocarbon group, or to bond all the bonds 1a to 4a to the same aromatic hydrocarbon group.
Further, it is preferable that the binding site between the bond 1a and the bond 2a and the binding site between the bond 3a and the bond 4a in ^{X 1 are located adjacent to each other in the aromatic hydrocarbon group.}
In the present specification, the existence of two binding sites at adjacent positions in a ring structure means that a ring member in the ring structure in which a certain binding site is present and a ring member in the ring structure in which another binding site is present are defined. It means that it is an adjacent ring member in the ring structure. For example, when the ring structure is a benzene ring structure, the adjacent position is the ortho position.

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

In formulas (A-1) to (A-5), ^RA11 to ^RA14 , ^RA21 to ^RA24 , ^RA31 to ^RA38 , ^RA41 to ^RA48 and ^RA51 to ^RA58 are independent hydrogen atoms. , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and ^LA31 and ^LA41 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene ^group, two of R A11 ^{~ R ^A14,} two of R A21 ^{~ R A24} , 2 of ^RA31 to ^RA38 , 2 of ^RA41 to ^RA48 , and 2 of ^RA51 to ^RA58 are binding sites with the carbonyl group in the above formula (1-1). Often, * represents the site of connection with other structures independently.

In the formula (A-1), ^RA11 to ^RA14 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and hydroxy. It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. An alkoxy group of 6 and an alkyl group having 1 to 3 carbon atoms are more preferable, and an alkyl group having a hydrogen atom or 1 to 6 carbon atoms is more preferable.
Examples ^{of the halogen atom in the alkyl halide group in RA11} to ^RA14 or the halogen atom include 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.
Further, it is preferable that two * in the formula (A-1) and two of ^RA11 to ^RA14 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. It is more preferable that *, ^RA12 and ^RA14 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-1), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.

Wherein ^{(A-2), R A21} ~ R A24 are each synonymous with ^R A11 ^{~ R A14} in formula (A-1), a preferable embodiment thereof is also the same.
Further, it is preferable that two * in the formula (A-2) and two of ^RA21 to ^RA24 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. It is more preferable that *, ^RA22 and ^RA24 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-2), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.

In the formula (A-3), ^RA31 to ^RA38 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and hydroxy. It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. An alkoxy group of 6 or an alkyl halide having 1 to 3 carbon atoms is more preferable, and an alkyl group having a hydrogen atom or 1 to 6 carbon atoms is more preferable.
Examples ^{of the halogen atom in the alkyl halide group in RA31} to ^RA38 or the halogen atom include 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.
Further, it is preferable that two * in the formula (A-3) and two of ^RA31 to ^RA38 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. ^*, one of R A31 ^{~ R A34,} ^and, more preferably one of R A35 ^{~ R A38} is a bonding site with the carbonyl group in the formula (1-1), two *, R ^{It is more preferable that A31} and ^RA38 are binding sites for the carbonyl group in the above formula (1-1). Further, in the formula (A-3), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
In the formula (A-3), ^LA31 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 is preferable, and a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, an -O- or a heterocyclic group. Is preferable, and it is more preferable to represent a single bond or —O—.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is a divalent aromatic hydrocarbon. It is preferably a group.
As the heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable. More preferably, 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 morpholin ring. These heterocycles may further form a fused ring with another heterocycle or hydrocarbon ring.
The number of ring members of the heterocycle is preferably 5 to 10, and more preferably 5 or 6.
The hetero atom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the halogen atom in the halogenated alkylene group include 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.

Wherein ^{^{(A-4), R A41}} ~ R A48, L A41 have the same meanings as ^R ^A31 ^~ ^R ^{A38, L} A31 in formula (A-3), preferable embodiments thereof are also the same.
Further, it is preferable that two * in the formula (A-4) and two of ^RA41 to ^RA48 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. It is more preferable that one of R ^A41 to R ^A44 and one of R ^A45 to R ^A48 are the binding sites with the carbonyl group in the above formula (1-1), and two * and R ^{It is more preferable that A41} and ^RA48 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-4), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.

Wherein ^{(A-5), R A51} ~ R A58 are each synonymous with ^R A11 ^{~ R A14} in formula (A-1), a preferable embodiment thereof is also the same.
Further, it is preferable that a total of four of the two * in the formula (A-5) and two of ^RA51 to ^RA58 are binding sites with the carbonyl group in the above formula (1-1), and two *, one of R ^A51 ~ ^{R A54,} ^and, more preferably one of R A55 ^{~ R A58} is a bonding site with the carbonyl group in the formula (1-1), two ^{*, R A52} and It is more preferable that ^RA56 is a binding site with a carbonyl group in the above formula (1-1). Further, in the formula (A-5), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.

Among these, X ¹ is preferably a group represented by the following formula (X-1) or the following formula (X-2).

In formula (X-1), ^RX11 and ^RX12 ^{are synonymous with RA11} ^{and RA13} in formula (A-1), respectively, and preferred embodiments are also the same.
Wherein ^{(X-2), R X21} ~ R X26, ^{and, L X21} ^{^R} A32 ^~ ^R ^A37 in each formula (A-3), and ^has the same meaning as ^{L A31,} preferable embodiments thereof are also the same.
In formula (X-1) or formula (X-2), of the two *, one is the binding site with the above-mentioned bond 1a and the other is the binding site with the above-mentioned bond 2a. , One shows the binding site with the above-mentioned binding 3a, and the other shows the binding site with the above-mentioned binding 4a.

^{Specific examples of the tetravalent group represented by X 1} in the formula (1-1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. .. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is synonymous with ^{X 1} in equation (1-1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride , 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane- 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 at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms are exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

-G ¹ , G ^2-
It is preferable that G ¹ and G ^{2 are independent substituents.}
Examples of the substituent in G ¹ and G ² include a group containing a polymerizable group or an organic group which may contain a hetero atom, and is poly from the viewpoint of chemical resistance, developability and solvent solubility of a specific resin. A group containing an alkyleneoxy group is preferable.

<< Groups containing polymerizable groups >>
As the ^{polymerizable group contained in the group containing a polymerizable group in G 1} or G ² , a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group or an alkoxymethyl group is preferable, and a vinyl group and a (meth) allyl group are preferable. Groups, (meth) acrylamide groups, (meth) acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups or alkoxymethyl groups are more preferred, and (meth) acryloxy groups, (meth) acrylamide groups, epoxys. Groups, methylol groups or alkoxymethyl groups are more preferred.
The number of polymerizable groups contained in the group containing the polymerizable group is 1 or more, preferably 1 to 15, more preferably 1 to 10, and 1 to 5. More preferably, 1 or 2 is particularly preferable, and 1 is most preferable.

The group containing the above-mentioned polymerizable group is preferably a vinyl group, an allyl group, a (meth) acryloyl group, or a group represented by the following formula (III).

In formula (III), ^R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.

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 has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable). The (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. Such as alkylene group, —CH ₂ CH (OH) CH ₂ −, and ethylene group, propylene group, trimethylene group, −CH ₂ CH (OH) CH ₂ − are more preferable.
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.

<< Organic groups that may contain heteroatoms >>
The organic group that may contain a hetero atom is preferably an organic group that does not have a polymerizable group.
Examples of the hetero atom in the organic group which may contain the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like, and an oxygen atom is preferable.
Further, the hetero atom is preferably contained as an ether bond (—O—).
The organic group which may contain a heteroatom is preferably an organic group having 1 to 30 carbon atoms which may contain a heteroatom, and preferably an organic group having 2 to 20 carbon atoms which may contain a heteroatom. More preferred.

<<< Polyalkyleneoxy group >>>
Among these, the organic group that may contain the heteroatom is preferably an organic group having a polyalkyleneoxy group.

In the present invention, the 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 a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. Preferably, 2 is most preferred.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyloxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups from the viewpoint of achieving both solvent solubility and chemical resistance. A group bonded to the propyleneoxy group of the above is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

The organic group having a polyalkyleneoxy group is preferably a group represented by the following formula (PO-1).

Wherein ^{(PO-1), R P1} each independently represent an alkylene ^{group, R P2} represents a monovalent organic group, n represents an integer of 2 or ^{more, L P1} is connected a single bond or a divalent A group is represented, and * represents a binding site with an oxygen atom to which ^{G 1} or G ^{2 in the formula (1-1) is bonded.}

Wherein ^{(PO-1), R P1} each independently is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, an ethylene group (-CH ₂ -CH _2- ) or propylene group (-CH _2- CH (CH ₃ )-or-CH (CH ₃ ) -CH _2- ) is more preferable, and an ethylene group is further preferable.

In the formula (PO-1), ^RP2 represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group, or a group containing a polymerizable group, and is preferably an alkyl group. Is more preferable.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an ethyl group is further preferable.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
As the aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
As the polymerizable group contained in the above-mentioned group containing a polymerizable group, an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group and a (meth) acrylamide group are preferable. Groups, (meth) acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups or alkoxymethyl groups are more preferred, with (meth) acryloxy groups, (meth) acrylamide groups, epoxy groups, methylol groups or alkoxy. Methyl groups are more preferred.
As the group containing the above-mentioned polymerizable group, a group represented by the formula (P-1) described later is preferable, and a group represented by the formula (P-2) described later or the formula (P-3) described later is used. Is more preferable.

In the formula (PO-1), n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.

In the formula (PO-1), ^LP1 represents a single bond or a divalent linking group, and a single bond is preferable.
As the divalent linking group, 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 is preferable, and a hydrocarbon group, an ether bond, or a carbonyl group is preferable. A group, -NR ^N- , or a group in which two or more of these are bonded is more preferable, and a hydrocarbon group, an ester bond, an amide bond, a urethane bond, a urea bond, or a group in which two or more of these are combined is further preferable.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The hydrocarbon group represented by L ^P1, 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 Preferably, 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 the benzene ring, or a group represented by a bond thereof.

<<< Hydrocarbon groups substituted with halogen atoms >>>
Further, from the viewpoint of solvent solubility and ring closure, the organic group which may contain a hetero atom may be a hydrocarbon group substituted with a halogen atom.
Examples of the halogen atom in the hydrocarbon group substituted with the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
As the hydrocarbon group, an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group is more preferable.
As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 2 to 4 carbon atoms is further preferable.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable.
That is, the hydrocarbon group substituted with a halogen atom is preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
By ^{including the hydrocarbon group substituted with a halogen atom as the G 1} or the G ² , the film strength of the obtained cured film is improved.

<< Other Substituents >>
The G ¹ or G ² may be another substituent.
Examples of other substituents include hydrocarbon groups having an acid group and the like.
Examples of the hydrocarbon group having an acid group include an alkyl group having an acid group, an aromatic hydrocarbon group having an acid group, and an aralkyl group having an acid group.
As the alkyl group in the alkyl group having an acid group, an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
Examples of the acid group in the alkyl group having an acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and a carboxy group is preferable. As the group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
As the aralkyl group having an acid group, an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
Examples of the acid group in the aromatic hydrocarbon group having the acid group or the aralkyl group having the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and phenol. A sex hydroxy group or a carboxy group is preferable, and a phenolic hydroxy group is more preferable. Among these, an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferable, and an aromatic having a phenolic hydroxy group is preferable. A group hydrocarbon group or an aralkyl group having a phenolic hydroxy group is more preferable, and a phenyl group having a phenolic hydroxy group or a benzyl group having a phenolic hydroxy group is further preferable.

From the viewpoint of ring closure rate and chemical resistance, an ethylenically unsaturated group with respect to the total molar amount of ^{G 1} and G ^{2 in} the repeating unit represented by the formula (1-1) contained in the specific resin. The ratio of the molar amount of the ^{above G 1} or the above G ² which is a substituent containing the above is preferably 0 to 30%.
From the viewpoint of the ring closure rate, the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%.
From the viewpoint of chemical resistance, the above ratio is preferably 10 to 30%, more preferably 15 to 30%.

From the viewpoint of ring closure rate, chemical resistance and solvent solubility of the specific resin, all the molars of G ¹ and G ^{2 in} the repeating unit represented by the above formula (1-1) contained in the above resin. The ratio of the molar amount of the ^{G 1} or the G ² which is an organic group having 1 to 30 carbon atoms which may contain a hetero atom to the amount is preferably 20 to 100%.
From the viewpoint of the ring closure rate, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more. It is preferably 70% or more, and most preferably 70% or more.
From the viewpoint of chemical resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and more preferably 80% or less. It is particularly preferable, and most preferably 70% or less.

From the viewpoint of ring closure rate, chemical resistance and solvent solubility of the specific resin, all the molars of G ¹ and G ^{2 in} the repeating unit represented by the above formula (1-1) contained in the above resin. The ratio of the molar amount of the ^{G 1} or the G ² which is an organic group having a polyalkylene oxy group to the amount is preferably 20 to 100%.
The organic group having a polyalkyleneoxy group in the above ratio description may be an organic group further containing a polymerizable group as long as it is an organic group containing a polyalkyleneoxy group, but contains a polyalkyleneoxy group. Moreover, it is preferably an organic group having no polymerizable group.
From the viewpoint of the ring closure rate, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more. It is preferably 70% or more, and most preferably 70% or more.
From the viewpoint of chemical resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and more preferably 80% or less. It is particularly preferable, and most preferably 70% or less.

-Y ^1-
In formula (1-1), Y ¹ represents an n + divalent group containing an aromatic hydrocarbon group.
Aromatic hydrocarbon group for Y ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, 2 or more benzene rings It is more preferable that the group has the hydrogen atom removed from the group, and it is particularly preferable that the group has 3 or more hydrogen atoms removed from the benzene ring.
In the formula (1-1), in Y ^1, binding site of the two nitrogen atoms according to formula (1-1) is preferably either an aromatic hydrocarbon group. That is, the two nitrogen atoms according to formula (1-1), an aromatic hydrocarbon ring structure contained in Y ^1, it is preferable to directly bond.
In the formula (1-1), in ^{Y 1,} binding site of the ^{A 1} is preferably either an aromatic hydrocarbon group. That is, it is preferable that A ¹ is directly bonded to the aromatic hydrocarbon ring structure contained ^{in Y 1.}

Y ¹ preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and the above formulas (A2-1) to Y1. It is more preferable that the structure is at least one selected from the group consisting of the structures represented by the formula (A2-5).

Wherein ^{(A2-1) ~ (A2-5),} R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and ^{^R} A251 ^~ ^R ^A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and ^LA231 and ^LA241 are independently single-bonded, carbonyl group, sulfonyl group and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene ^group, at least one of R A211 ^{~ R ^A214,} at least one of R a 221 ^{~ R A224} ^one, at least one of ^R A231 ^~ R ^{^A238,} at least one of R a 241 ^{~ R A248,} ^and, at least one of ^R A251 ^~ R ^A258 is between ^{a 1} in the formula (1-1) It may be a binding site, and each independently represents a binding site with another structure.

Among these, from the viewpoint of solvent solubility, Y ¹ preferably contains a structure represented by any of the formulas (A2-1) to (A2-4), and is preferably the formula (A2-2) or the formula (A2-2). It is more preferable to include the structure represented by any one of A2-4).

In the formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 are the above formulas (1-). 1) free of attachment to the carbonyl group in at ^least one of R A211 ^{~ R ^A214,} at least one of R a 221 ^{~ R ^A224,} at least one of ^{^{R A231 ~ R A238, R A241}} ~ at least one of R ^A248, ^and, at least one of ^R A251 ^~ R ^A258 may be binding sites for ^{a 1} in the formula (1-1), except that each of above formula (a-1) in ~ ^(a-5), have the same meaning as ^{^{^{^{R A11 ~ R A14, R A21}}}} ~ R A24, R A31 ~ R A38, R A41 ~ R A48 and ^{^R} A51 ^~ ^R ^A58, preferred The aspect is also the same.

In formula ^(A2-1), at least one of ^R A211 ^~ R ^A214, is preferably a binding site to the ^{A 1} in the formula ^(1-1), one of the A of ^R A211 ^~ R ^A214 more preferably a binding site with ^1, it is preferred that R ^A213 is a bond site of the a ^1.
In formula ^(A2-2), at least one of R A 221 ^{~ R A224,} is preferably a binding site to the ^{A 1} in the formula ^(1-1), one of the A of ^R A221 ^~ R ^A224 more preferably a binding site with ^1, it is preferred that R ^{a 223} is a binding site for the a ^1.
In formula ^(A2-3), at least one of ^R A231 ^~ R ^A238, is preferably a binding site to the ^{A 1} in the formula ^(1-1), two of ^R A231 ^~ R ^A238, the more preferably a binding site to the a ^{^1,} bract one of ^R A231 ^~ R ^{^A234,} more preferably two one meter of the ^R A235 ^~ R ^A238 is a binding site to the ^{a 1,} R ^A231 and two of ^{R A238,} it is particularly preferably a binding site between the ^{a 1.}
In formula ^(A2-4), at least one of R A 241 ^{~ R A248,} is preferably a binding site to the ^{A 1} in the formula ^(1-1), two of ^R A241 ^~ R ^A248, the more preferably a binding site to the a ^{^1,} bract one of ^R A241 ^~ R ^{^A244,} more preferably two one meter of the ^R A245 ^~ R ^A248 is a binding site to the ^{a 1,} R ^A241 and two of ^{R A248,} it is particularly preferably a binding site between the ^{a 1.}
In formula ^(A2-5), at least one of ^R A251 ^~ R ^A258, is preferably a binding site to the ^{A 1} in the formula ^(1-1), two of ^R A251 ^~ R ^A258, the more preferably a binding site to the a ^{^1,} bract one of ^R A251 ^~ R ^{^A254,} more preferably two one meter of the ^R A255 ^~ R ^A258 is a binding site to the ^{a 1,} R ^A253 and two of ^{R A257,} it is particularly preferably a binding site between the ^{a 1.}

In formulas (A2-1) to (A2-5), it is preferable that each of the two *'s is a binding site with a nitrogen atom to which ^{Y 1 in formula (1-1) binds.} ^{That is, the two nitrogen atoms to which Y 1} in the formula (1-1) is bonded can be directly bonded to the positions represented by two * in the formulas (A2-1) to (A2-5). preferable.

Among these, Y ¹ is preferably a group represented by the following formula (Y-1) or (Y-2).

Wherein ^{^{(Y-1), R Y11}} , R Y12, R Y13 each has the same meaning as ^R ^{A211, R A212} and ^{R A214} in formula (A2-1), preferable embodiments thereof are also the same.
Wherein ^(Y-2), each of ^R Y21 ^~ R ^Y26, have the same meanings as ^{^R} A242 ^~ ^R ^A247 in formula (A2-4), preferable embodiments thereof are also the same.
Formula (Y-1) or Formula (Y-2) in a binding site to the nitrogen atom * each, ^{where Y 1} in the formula (1-1) are attached # respectively, equation (1-1) the binding site of the a ¹ in, respectively.

The specific resin contains at least one structure selected from the group in which the above-mentioned X ¹ in the formula (1-1) consists of the structures represented by the formulas (A-1) to (A-5). Moreover, it is preferable that Y ¹ contains at least one structure selected from the group consisting of the structures represented by the formulas (A2-1) to (A2-5).
Further, the specific resin has at least one structure selected from the group in which the above-mentioned X ¹ in the formula (1-1) consists of the structures represented by the formulas (A-1) to (A-5). It is more preferable that Y ¹ is at least one structure selected from the group consisting of the structures represented by the formulas (A2-1) to (A2-5).
The preferred embodiment of the structure represented by each of these equations is as described above.

-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, a methylol group or an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide group are preferable. A group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
The number of polymerizable groups contained in A ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. It is particularly preferable to have one or two, and most preferably one.

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 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 the 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, preferably a single bond. A bond, or 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 preferable.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The hydrocarbon group represented by L ^1, 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 Preferably, 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 the benzene ring, or a group represented by a bond thereof.

In formula (P-1), A ² is a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group. Groups are preferred, with (meth) acryloxy groups, (meth) acrylamide groups, epoxy groups, methylol groups or alkoxymethyl groups being more preferred.

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

Further, A ¹ is preferably a group represented by the following formula (P-2) or formula (P-3).

In formula (P-2), A ² represents a polymerizable group, and * represents a binding site with ^{Y 1.}
Wherein ^{(P-2), A} 2 has the same meaning as ^{A 2} in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), A ² represents a polymerizable group, and L ² is a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N- , or. These represent a group in which two or more are bonded, Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents a bond site with ^{Y 1.} ^RN is as described above.
Wherein (P-3), ^{A 2} has the same meaning as ^{A 2} in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), L ² is preferably a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof. The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group.
As used herein, the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. Further, in the present invention, the polyalkyleneoxy group means 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 a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
As the alkylene group, an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 1 to 10 carbon atoms is further preferable.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable. Especially preferable.
As the alkylene group in the (poly) alkyleneoxy group, an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, an ethylene group or a propylene group is more preferable, and an ethylene group is further preferable. ..
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. preferable.
In the formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
In the present invention, when simply describing "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 binding site with L ² ^{in Z 1} may be a carbon atom in the ester bond or an oxygen atom.

-N-
In the 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 further preferably an integer of 1 to 4. It is preferably 1 or 2, and most preferably 1.
Further, when n is an integer of 2 or more, n pieces of A ¹ may each be the same or may be different.

^{The structure represented by Y 1} , A ¹ and n in the formula (1-1) is preferably a structure derived from a diamine.
As such a diamine, a diamine represented by the following formula (DA-1) is preferable, and specifically, diamines (AA-1) to diamines (AA-8) synthesized in Examples described later are preferable. Can be mentioned.

In formula (DA-1), Y ¹ , A ¹ ^{, and n are synonymous with Y 1} , A ¹ , and n in formula (1-1), respectively, and the preferred embodiments are also the same.

-Content of repeating unit represented by formula (1-1)-
The content of the repeating unit represented by the formula (1-1) in the specific resin is 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more, based on all the repeating units of the specific resin. The above is more preferable, and 80 mol% or more is particularly preferable. The upper limit of the content is not particularly limited, and may be 100 mol% or less.
The content of the repeating unit represented by the formula (1-1) in the specific resin is preferably 50% by mass or more, more preferably 60% by mass or more, based on the mass of the specific resin. It is more preferably 70% by mass or more, and particularly preferably 80% 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 one type of repeating unit represented by the formula (1-1) alone, or may contain two or more types of repeating units represented by the formula (1-1) having different structures. When the specific resin contains two or more repeating units represented by the formula (1-1) having different structures, the total content of the repeating units represented by the formula (1-1) contained in the specific resin is , It is preferable that the content is within the above range.

[Other repeating units]
-Repeating unit represented by equation (1)-
The specific resin may further contain other repeating units.
Examples of the other repeating unit include a repeating unit represented by the following formula (1).
The repeating unit corresponding to the repeating unit represented by the above formula (1-1) shall not correspond to the 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 the main chain.

In formula (1), A ^A1 and A ^A2 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 independently represents a hydrogen atom or a monovalent organic group.

In the formula (1), A ^A1 and A ^A2 independently represent an oxygen atom or -NH-, and are preferably oxygen atoms.
In the formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both are polymerizable. More preferably, it contains a group.
The polymerizable group in R ¹¹³ or ^{R 114,} include the same groups as the polymerizable group in ^{A 1} in the above formula (1-1).
Further, ^{as the monovalent organic group in R 113} and R ¹¹⁴ ^{, a group containing a polymerizable group in G 1} and G ² in the above formula (1-1), an organic group which may contain a hetero atom, or an organic group may be contained. Other substituents are also preferably mentioned.

In the formula (1), the structure of R ¹¹⁵ is preferably the same as that ^{of X 1} in the formula (1-1). The preferred embodiment of R ^{115 is the same as} the preferred embodiment of X ¹ described above.
Further, in R ¹¹⁵ , the binding site with the four carbonyl groups in the formula (1-1) may have an aliphatic hydrocarbon ring structure.
When R ¹¹⁵ has an aliphatic hydrocarbon ring structure ^{, examples of R 115} include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Anhydrous, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxohydrocarbon-3yl) -3-methylcyclohexene-1,2-dicarboxylic acid anhydride ( DOCDA), 4- (2,5-dioxohydrocarbon-3-yl) -tetraline-1,2-dicarboxylic acid anhydride and the like can be mentioned.

In the formula (1), R ¹¹¹ preferably has a structure containing no polymerizable group.
In addition, R ¹¹¹ has an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups bonded to at least one of an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR ^N- . It is preferably a group. ^RN is as described above.
As the aliphatic hydrocarbon group, an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms is preferable, and an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms is more preferable.
Further, as the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aliphatic hydrocarbon group having 6 to 12 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.
Among these, from the viewpoint of solvent solubility, R ¹¹¹ 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.

^{Further, R 111} in the formula (1) is preferably represented by ^{−Ar 0} −L ⁰ −Ar ⁰ − from the viewpoint of the flexibility of the obtained cured film. 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), and a phenylene group is preferable. L ⁰ ^{has the same meaning as LA 31} in the above formula (A-3), and the preferred embodiment is also the same.

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

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.

The ^{monovalent organic group of R 50} to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

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

^{R 111} in the formula (1) preferably has a structure derived from a diamine.
Examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diamino. Cyclopentane, 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 paraphenylenediamine, diaminotoluene, 4,4'-or 3,3'- Diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-or 3,3'-diaminodiphenylmethane, 4,4'-or 3,3'-diaminodiphenylsulfone, 4,4 '-Or 3,3'-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-aminophenyl) propane, 2,2-bis (3-Hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, Bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 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-a) Minophenoxy) 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- (4- (4-) Aminophenoxy) Phenyl] Hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'- Tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-Dimethyl-3,3'-diaminodiphenylsulfone,3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2 , 4- or 2,5-diaminocumen, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine , 4,6-Dihydroxy-1,3-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ) Ethan, diaminobenzanilide, diaminobenzoic acid, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis ( 4-Aminophenyl) Octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-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-dimethyl Phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoro) Methyl) phenyl] Hexafluoropropane, Parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4,4'-bis (methyl) phenyl] 4-Amino-3-trifluoromethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethyl) Phenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diamino Biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl At least one diamine selected from.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and the diamine is more preferably the diamine and does not contain an 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, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.

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.

Examples of the diamine giving the structure of the above formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and the like. Examples thereof include 2,2'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

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

Further, for the purpose of improving the adhesion to the base material, a diamine having a siloxane structure such as bis (3-aminopropyl) tetramethyldisiloxane or bis (paraaminophenyl) octamethylpentasiloxane may be used as the diamine component. Good.

<< Content >>
The total content of the repeating units represented by the formula (1) in the specific resin is not particularly limited, but is preferably 30% by mass or less, and preferably 20% by mass or less, based on the total mass of the specific resin. More preferably, it is 10% by mass or less. The lower limit of the total content is not particularly limited, and may be 0% by mass or more.
Further, from the viewpoint of chemical resistance of the obtained cured film, it is also preferable that one aspect of the specific resin is a mode that does not substantially contain the repeating unit represented by the formula (1).
In this case, the total content of the repeating units represented by the formula (1) is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the specific resin. It is more preferably mass% or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The specific resin may contain one type of repeating unit represented by the formula (1) alone, or may contain two or more types of repeating units represented by the formula (1) having different structures. When the specific resin contains two or more repeating units represented by the formula (1) having different structures, the total content of the repeating units represented by the formula (1) contained in the specific resin is the above-mentioned content. It is preferable that it is included in the range of.

-End structure-
The structure of the terminal of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, the terminal is an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. It may be sealed with. Of these end-capping agents, it is preferable to use monoalcohol, phenol, thiol, thiophenol, and monoamine.
Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol, and isopropanol. , 2-Butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantan alcohol and other tertiary alcohols, and the like. Preferred compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like.
Examples of 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 Aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid , 3-Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.
Further, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for amino groups include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride and the like, and carboxylic acid anhydride and carboxylic acid chloride are more preferable. preferable. Preferred compounds of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride and the like. Preferred compounds of carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantancarbonyl 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 is 20% by mass or more with respect to the total solid content of the curable resin composition from the viewpoint of improving the breaking elongation of the obtained cured film. It is preferably 30% by mass or more, more preferably 40% by mass or more.
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, from the viewpoint of improving the resolution of the curable resin composition. It is more preferably less than or equal to 97% by mass or less, and even more preferably 95% by mass or less.

[Physical characteristics 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, and even more preferably 4,000 to 50,000.
The degree of dispersion of the molecular weight of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
From the viewpoint of developability, the degree of dispersion of the molecular weight of the specific resin is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is further preferable.

-Acid value-
The acid value of the specific resin is preferably 0 to 2.0 mmol / g, more preferably 0 to 1.5 mmol / g, and even more preferably 0 to 1.0 mmol / g.
When the curable resin composition is used for alkaline development 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, 2 It is 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.
The acid group refers to a group neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, 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.
Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and the like, and a carboxy group is preferable.

-Polymerizable base value-
The molar amount of the polymerizable group (polymerizable base value, unit is mmol / g) contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, and is 0.1 to 5 mmol / g. Is more preferable.
The polymerizable group is contained in, for example, A ¹ , G ¹ , G ^{2 and the} like in the repeating unit represented by the formula (1-1).
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 mmol / g, and 0.1 to 0.1 to g. More preferably, it is 5 mmol / g.
When the specific resin contains a polymerizable group such as a cyclic ether group, a methylol group, or an alkoxymethyl group as a polymerizable group, the molar amount of the polymerizable group contained in 1 g of the specific resin is 0.05 to 10 mmol / g. It is preferably 0.1 to 5 mmol / g, and more preferably 0.1 to 5 mmol / g.

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

〔Production method〕
The specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.
Further, in the method for producing the specific resin, a diamine is reacted with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the above-mentioned tetravalent carboxylic acid compound. It is preferable to include a step of causing the compound (precursor production step).

-Precursor manufacturing process-
Examples of the diamine used in the precursor production step include the diamine represented by the above formula (DA-1).
Further, by further using the diamine described in the description of the formula (1), the repeating unit represented by the formula (1) can be introduced into the specific resin.
The tetravalent carboxylic acid compound used in the precursor production step may be a carboxylic acid dianhydride, or two of the four carboxy groups are modified by esterification, halogenation or the like. It may be a compound having a different structure. Preferably, a compound in which two of the four carboxy groups are esterified can be mentioned.
It is preferable that ^{G 1} and G ² in the above formula (1-1) are introduced by the above esterification.
Further, it is preferable that the compound in which two of the above four carboxy groups are esterified is halogenated with a halogenating agent and then reacted with a diamine.
In addition, the reaction conditions in the precursor production step can be appropriately determined with reference to known esterification conditions.

Further, in the precursor production step, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

The precursor manufacturing step preferably includes a step of precipitating a solid. Specifically, the specific resin in the reaction solution can be precipitated in water, and a polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

-Diamine manufacturing process-
The method for producing the specific resin is a compound A having two nitro groups, at least one reactive group, and an aromatic hydrocarbon group, a group capable of forming a bond with the reactive group, and a polymerizable group. After reacting with compound B having compound A to obtain compound C in which compound A and compound B are bonded, a step of reducing the nitro group in compound C to obtain a diamine having an aromatic hydrocarbon group (diamine production step). ) May be included.
The diamine obtained in the diamine production process is used as the diamine in the precursor production process.

The reactive group in compound A is not particularly limited, and examples thereof include an amino group, a hydroxy group, and a carboxy group.
Compound A preferably has a structure in which two nitro groups and at least one reactive group are directly bonded to the aromatic hydrocarbon group.

The group capable of forming a bond with the reactive group in the compound B is not particularly limited, and examples thereof include a hydroxy group, a carboxy group, a carboxylic acid halide group, an epoxy group, and an isocyanate group.
The polymerizable group in the compound B, include exemplified groups as the group included in A ¹ in the above equation (1-1).

Compound C is a group obtained by reacting compound A with compound B, and is a compound having two nitro groups and a group containing at least one polymerizable group.
A diamine compound is obtained by reducing the nitro group in compound C.
As the reduction method, known methods such as Beshan reduction, hydrogenation reaction using a metal catalyst such as palladium, platinum and nickel and a hydrogen source such as hydrogen gas and ammonium formate, and a reduction method using metal hydride as a reducing agent are used. be able to.

For example, the synthesis of the dinitro compound (A-1) in the examples described later is compound C by reacting compound A 3,5-dinitrobenzoyl chloride with compound B 2-hydroxyethyl methacrylate. This is a reaction for obtaining a dinitro compound (A-1).
Further, the synthesis of diamine (AA-1) in the examples described later is a reaction of reducing two nitro groups in the dinitro compound (A-1) which is compound C to obtain diamine (AA-1).

<Photosensitizer>
The curable resin composition of the present invention contains a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.

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

The photoradical polymerization initiator contains at least one compound having a molar extinction 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 preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (for example, 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 and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

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

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

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

As the aminoacetophenone-based initiator, commercially available products 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, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

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

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

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = NOC (= O)-in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound 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 the compound (C-3) described in paragraph 0101 of JP-A-164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization 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. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In the formula (I), ^RI00 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, and the like. 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, or a carbon number interrupted by one or more oxygen atoms. 2 to 18 alkyl group and at least one substituted phenyl group or a biphenyl group of the alkyl group having 1 to 4 carbon ^atoms, or ^{R I01} is a group represented by the formula ^{(II), R I00} R ^I02 to R ^I04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.

In the formula, R ^I05 to R ^I07 are the same as ^{R I 02} to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.

When the photopolymerization initiator is contained, the content thereof 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 even 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 kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

[Photoacid generator]
Further, the curable resin composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing the photoacid generator, for example, acid is generated in the exposed part of the curable resin composition layer, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part becomes A positive relief pattern that is removed by the developer can be obtained.
Further, when the curable resin composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the cross-linking reaction of the polymerizable compound is caused by the acid generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.

The quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and a sulfonamide bond. Examples thereof include those bonded by at least one of the above. 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, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl 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-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

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

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699. (Manufactured by Kojunyaku Co., Ltd.) and the like.

When a photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, preferably 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 further 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 in the above range.

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

The number of radically polymerizable groups contained in 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 preferably has three or more radically polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radically 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 bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound. For example, the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
On the other hand, from the viewpoint of developability, the curable resin composition is particularly preferably a compound having two radically polymerizable groups.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogeno group. Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (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, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as preferred radically polymerizable compounds other than the above, those described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having the above, or a cardo resin.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, Japanese Square Root 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radically polymerizable compounds, and their contents are incorporated in the present specification.

Examples of radically polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku (commercially available). Manufactured by A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd., Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa ( Meta) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups contain ethylene glycol residues or propylene glycol residues. A structure that is bonded via a structure is preferable. These oligomer types can also be used.

Commercially available products of the radically polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains. , 231, 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry 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.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, 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. It 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, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include 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 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. On the other hand, from the viewpoint of the development speed in the case of alkaline development, the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. Moreover, the polymerizability is good. The acid value is measured according to the description of JIS K 0070: 1992.

For the curable resin composition of the present invention, it is preferable to use bifunctional metaacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate having a formula of polyethylene glycol chain). About 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-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct of bisphenol A Diacrylate, EO adduct dimetallilate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimetallilate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate Isocyanuric acid-modified dimethacrylate, other bifunctional acrylate having a urethane bond, and bifunctional methacrylate having a urethane bond can be used. If necessary, two or more of these can be mixed and used.
From the viewpoint of suppressing warpage associated with the control of the elastic modulus of the cured film, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. Examples of the monofunctional radical polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (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 and the like (meth) ) Acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used. As the monofunctional radical 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.
Further, as the bifunctional or higher-functional polymerizable compound, allyl compounds such as diallyl phthalate and triallyl trimellitate may be used.

[Polymerizable compounds other than the radically polymerizable compounds described above]
The curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group (methylol group), an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

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

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t-valence of 1 to 200 carbon atoms, and R ¹⁰⁵ is a group represented by -OR ¹⁰⁶ or -OCO-R ^107. R ¹⁰⁶ indicates a hydrogen atom or an organic group ^{having 1 to 10 carbon atoms, and R 107} indicates an organic group having 1 to 10 carbon atoms.

(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ is a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁴⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ^507. , R ⁵⁰⁶ represents a hydrogen atom or an organic group ^{having 1 to 10 carbon atoms, and R 507} represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diasetoxymethyl-p-cresol, etc. Be done.

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

-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 lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage 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 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi). Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trademark, manufactured by DIC Co., Ltd.), Epicron (registered trademark) EXA-830LVP , Epicron® EXA-8183, Epicron® EXA-8169, Epicron® N-660, Epicron® N-665-EXP-S, Epicron® N-740, Rikaresin (registered trademark) BEO-20E, Rikaresin (registered trademark) BEO-60E, Rikaresin (registered trademark) HBE-100, Rikaresin (registered trademark) DME-100, Rikaresin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd., EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), seroxide (registered trademark) 2021P, seroxide (registered trademark) 2081, seroxide (registered Trademarks) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide (registered trademark) PB3600 (trade name, manufactured by Daicel Co., Ltd.), 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 name, manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. .. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.

-Oxetane compound (compound having an oxetanyl group)-
Examples of the oxetane compound 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, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or Two or more kinds may be mixed.

-Benzodizepine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly. Examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

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

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, 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 (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include 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, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

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

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.

As sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like are preferable.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.

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- Consists of one 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 two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

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

The solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total amount is preferably in the above range.

<Thermal polymerization initiator>
The curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate 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 allowed to proceed in the heating step described later, so that the chemical resistance can be further improved.

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

When the thermosetting initiator is contained, the content thereof 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 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

<Thermal acid generator>
The curable resin composition of the present invention may contain a thermosetting agent.
The thermoacid generator generates an acid by heating, and is at least one compound selected from a compound 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. It has the effect of promoting the cross-linking reaction of methylol groups and the like contained in.
When the curable resin composition of the present invention contains a thermoacid generator, the specific resin preferably contains a methylol group or an alkoxymethyl group as a polymerizable group.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the curable resin composition is applied to the substrate and then dried (prebak: about 70 to 140 ° C.), and final heating (cure: about 100 to 400) after patterning in subsequent exposure and development It is preferable to select a thermosetting agent that generates an acid at (° C.)) because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935A.

Among them, those that generate alkyl sulfonic acid having 1 to 4 carbon atoms or haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the cured film and it is difficult to deteriorate the physical properties of the cured film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-tolyl) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as thermal acid generators.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the cross-linking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Further, from the viewpoint of electrical insulation of the cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Other resins>
The curable resin composition of the present invention may contain another resin (hereinafter, also simply referred to as “other resin”) different from the above-mentioned specific resin.
Examples of other resins include polyimide precursors of a type different from the specific resin.

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

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).

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

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

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

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

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.

The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

It is preferable to include a step of precipitating a solid in the production of the polyimide precursor. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

When the curable resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more with respect to the total solid content of the curable resin composition. It is more preferably 05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and 10% by mass or more. It is even more preferable to have.
The content of the other resin in the curable resin composition of the present invention is preferably 80% by mass or less, and preferably 75% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the curable resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the 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, and may be 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 kinds are included, the total amount is preferably in 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 contained as another resin, the curable resin composition preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion 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 it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermobase generator.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.

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

-Ammonium cation-
As the ammonium cation, a quaternary ammonium cation is preferable.
Further, 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 be bonded to each other to form a ring.

In the 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. It is more preferably 12 aryl groups. R ¹ to R ⁴ 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. Examples thereof include a carbonyl group and an acyloxy group.
When ^{at least two of R 1} to R ⁴ are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).

In the formula (Y1-1) and ^{(Y1-2), R 101} represents an n-valent organic group, ^{R 1} has the same meaning as ^{R 1} in the formula ^{(101), Ar 101} and ^{Ar 102} are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the 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. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.

-Anion-
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion. 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 carboxylic acid anion is preferably represented by the following formula (X1).

In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ C (= O) groups (σm = 0.63), and HC≡C groups (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 applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 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 carboxylic acid anion is preferably represented by the following formula (XA).

In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent connecting group selected from the group consisting a combination thereof, ^{R X} is , Hydrogen atom, alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.

From the viewpoint that the cyclization of the specific resin is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion. , It is preferable to contain an anion having a pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, and preferably -2 or more, from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific resin or the like is improved. Is more preferable.
The above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

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

[Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferable.
Further, 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 are bonded to each other to form a ring. It may be formed.
In the formula (102), R ⁵ and R ⁶ ^{are synonymous with R 1} to R ⁴ in the above formula (101), and the preferred embodiment is 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 a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.

The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).

In Formula ^{(Y1-3) ~ (Y1-5),} R 101 represents an n-valent organic group, ^{R 5} has the same meaning as ^{R 5} in the formula (102), ^{R 7} is R in the formula (102) ^{Synonymous with 7} , n represents an integer of 1 or more, and m represents an integer of 0 or more.
In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

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

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
Further, 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. It is more preferably an aryl group, and even 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. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and 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 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

[Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iodonium cation-
As the iodonium cation, a diallyl iodonium cation is preferable.
Further, 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. It is more preferably an aryl group, and even 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, and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and 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 synthetic suitability, they are preferably the same group.

[Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Phosnium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, 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.
Each of R ¹³ to R ¹⁶ is preferably an alkyl group or an aryl group independently, 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. It is more preferably an aryl group, and even 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. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and 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 synthetic 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 with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further 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, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

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

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present 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, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

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

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

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

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

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb ¹³ is preferably an arylalkyl group.

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

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

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further 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 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

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

Among the above-mentioned onium salts, the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.

The content of the thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

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

The migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenolic compounds , Pyrazole acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor 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 is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total amount is preferably in the above range.

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

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone. , 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine first cerium salt, N- Nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic 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 radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxyl An amine ammonium salt or the like is preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, 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 is, for example, 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. Further, when the storage stability of the photosensitive resin composition solution is required, an embodiment 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. Is.

The polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total amount is preferably in the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound. And so on.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride. 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-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Examples thereof include isocyanatepropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.

The content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. 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 good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total amount is preferably in the above range.

<Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, and a curing agent, if necessary. A curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an antioxidant and the like 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. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracene, anthracene, anthrapylidene, benzylidene, oxonol, pyrazole triazole azo, pyridone azo, Compounds such as cyanine-based, phenothiazine-based, pyropyrazoleazomethine-based, xanthene-based, phthalocyanine-based, penzopyran-based, and indigo-based 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-dimethylaminosinnamiridene indanone, p- Dimethylaminobenzylene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) isonaftthiazole, 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) ) Ethyl coumarin-3-carboxylate), 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, etc. Can be 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-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 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 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), a group of compounds having _{-S-S-, -SO 2-S-, -NO-, SH, PH, SiH, and GeH in the molecule.} ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xantate compound and the like having a thiocarbonylthio group used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.

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

When the curable resin composition of the present invention has 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. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total amount is preferably in the above range.

[Surfactant]
Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

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. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total amount is preferably in the above range.

[Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has 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 preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total amount is preferably in 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 coating surface properties.

The metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.

Further, 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. Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. Further, as the storage container, for the purpose of suppressing impurities from being mixed into the raw material and the curable resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a layered bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

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

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized 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. , 0.05 MPa or more and 0.3 MPa or less is more preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

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

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them 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, or 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. The laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. Further, it is preferable that the laminate of the present invention contains two or more cured films and includes 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 preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. A preferred embodiment is a film obtained by curing the 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. The compositions may be present or have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" published in November 2011 , Japan Polyimide / Aromatic Polymer Study Group / ed., "Latest Polyimide Basics and Applications" NTS, August 2010, etc. can be referred to.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing 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 preferable.
Further, the method for producing a cured film of the present invention further includes the film forming step, and further includes an exposure step for exposing the film and a developing step for developing the film (developing the film). Is more preferable.
Further, 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) Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) Exposure Development step of developing the developed film (d) Heating step of heating the developed film at 50 to 450 ° C. By heating in the heating step, the curable resin composition layer after development is further added. Can be cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.

The 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. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, 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 as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).

The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material and a molded resin base material are more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.

Further, when the curable resin composition layer is formed on the surface of the resin layer such as the curable resin composition layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

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

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, application is performed at a rotation speed of 300 to 3,500 rpm 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. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.

<Drying process>
The production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. If the amount of solvent in the composition is large, vacuum drying and heat drying can also be combined. A hot plate, a hot air oven, or the like is used for heat drying, and the heating and drying 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 determined as long as the curable resin composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with 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 wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples include laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, etc. (7) second harmonic 532 nm of YAG laser and third harmonic 355 nm. The curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) 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 developing step of performing a developing process on the exposed film (curable resin composition layer). By developing, for example, in the case of a negative type photosensitive resin composition, an unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.

Development is carried out using a developing solution. If the curable resin composition is a negative type curable resin composition, the developing solution is such that the unexposed portion (non-exposed portion) of the curable resin composition layer is removed, which is the curability of the present invention. If the resin composition is a positive curable resin composition, those from which the exposed portion (exposed portion) is 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 developing solution 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 developing solution. Is more preferable, and it is particularly preferable that the organic solvent is not contained.
The developing solution in alkaline development is more preferably an aqueous solution having a pH of 9 to 14.
Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine. 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 can be mentioned. Of these, an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
The alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total amount is preferably in the above range.

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

Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, 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 (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, 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. , Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatics such as toluene, xylene, anisole, etc. Hydrocarbons, cyclic terpenes such as limonene, and dimethyl sulfoxides are preferable as sulfoxides.

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

The developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

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

After the treatment with the developing solution, further rinsing may be performed.
In the case of solvent development, rinsing is preferably performed using an organic solvent different from the developing solution. For example, propylene glycol monomethyl ether acetate can be mentioned. The rinsing time is preferably 5 seconds to 5 minutes. Further, a step of applying both a developer and a rinse solution may be included between the development and the rinse. The time of the above step is preferably 1 second to 5 minutes.
In the case of alkaline development, rinsing is preferably performed using pure water.
The rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
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 this step includes a curing reaction of an unreacted polymerizable compound other than the specific resin, a curing reaction of an unreacted polymerizable group in the specific resin, and the like. Can be advanced with.
When the specific resin is a polyimide precursor and the curable resin composition contains a thermal base generator, in the heating step, for example, the thermal base generator decomposes to generate a base, and the polyimide precursor The 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, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is particularly preferable, 160 ° C. or higher is more preferable, and 170 ° C. or higher is most preferable. The upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. 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., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 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, and even more preferably 30 to 240 minutes.

Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that at this temperature, the polymerizable groups in the specific resin between the layers proceed with the cross-linking reaction.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in 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, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 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.

It is preferable that the heating step is performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing it under vacuum, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer forming process>
The 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 the development treatment.

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.

The method for forming the metal layer is not particularly limited, and an existing method 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, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

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

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once. Further, (c) the developing step may be followed by (e) a metal layer forming step, and (d) may be heated each time, or the layers may be laminated a predetermined number of times and then collectively (d). ) May be heated. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

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

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

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 the metal layer is provided. Specifically, a mode in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating 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 laminated alternately.

The present invention also discloses a semiconductor device containing the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are referred to. Yes, these contents are incorporated herein.

(resin)
The resin of the present invention preferably has a repeating unit represented by the following formula (1-1).

The above formula (1-1) has the same meaning as the formula (1-1) in the specific resin, and the preferred embodiment is also the same.
The resin of the present invention has the same meaning as the above-mentioned specific resin, and the preferred embodiment is also the same.

<Use>
The resin of the present invention is preferably used as the resin contained in the curable resin composition.
Further, in a composition in which a conventional polyimide is used, for example, a composition for an interlayer insulating film, a part or all of the conventional polyimide can be used in place of the resin of the present invention without particular limitation.
Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is required to have chemical resistance, for example, a composition for forming an insulating film, a composition for forming a laminate, and the like. It is considered that the composition is preferably used in the composition used for the purpose.

(Resin manufacturing method)
The method for producing a resin of the present invention comprises compound A having two nitro groups, at least one reactive group, and an aromatic hydrocarbon group, a group capable of forming a bond with the reactive group, and polymerization. A step of reacting a compound B having a sex group to obtain a compound C in which the compound A and the compound B are bonded, and then reducing the nitro group in the compound C to obtain a diamine having an aromatic hydrocarbon group (diamine). (Production step), and a step of reacting the diamine with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the tetravalent carboxylic acid compound. (Precursor production step), is preferably included.
The details of each of the above steps are as described in the method for producing a specific resin, and the preferred embodiments are also the same.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, "part" and "%" are based on mass unless otherwise specified.

(Synthesis of specific resin)
<Synthesis of diamine>
[Synthesis of dinitro compound (A-1)]
2-Hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 26.0 g (0.2 mol), dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in a flask equipped with a condenser and a stirrer. ) 17.4 g (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5 ° C. or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was dissolved in a flask over 1 hour using a dropping funnel. Dropped in. After completion of the dropping, the mixture was stirred at 10 ° C. or lower for 30 minutes, the temperature was raised to 25 ° C., and the mixture was stirred for 3 hours. Then, the reaction solution was _{diluted with 600 mL of ethyl acetate (CH 3} COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated aqueous sodium hydrogen carbonate, 300 mL of dilute hydrochloric acid, and saturated brine in that order. After the liquid separation washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 61.0 g of a dinitro compound (A-1). It was confirmed from the NMR spectrum that it was a dinitro compound (A-1). The dinitro compound (A-1) ^{was analyzed by 1 1} H-NMR. The results are shown below.
^{1 1} H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.97 (s, 3H), 4.55-4.57 (m, 2H), 4.70-4.73 (m, 2H), 5.63 (s, 1H), 6 .16 (s, 1H), 9.16-9.17 (d, 2H), 9.24-9.25 (d, 1H)
In the same manner, dinitro compounds (A-2) to (A-8) having the structures described later were synthesized.

<Synthesis of diamine (AA-1)>
In a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 5.9 g (110 mmol) of ammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ), Acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 3.0 g (50 mmol), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03 g Was weighed, 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added, and the mixture was stirred.
Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour, and the mixture was stirred for 30 minutes. Next, the outside temperature was raised to 85 ° C., stirred for 2 hours, cooled to 25 ° C. or lower, and then filtered using Celite (registered trademark). The filtrate was concentrated on a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separating funnel, washed twice with 300 mL of saturated aqueous sodium hydrogen carbonate, and then washed with 300 mL of water and 300 mL of saturated brine in that order. After the liquid separation washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 11.0 g of diamine (AA-1). It was confirmed from the NMR spectrum that it was a diamine (AA-1).
^{1 1} H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5 .58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H)
Similarly, diamines (AA-2) to (AA-8) having the following structures were synthesized by using dinitro compounds (A-2) to (A-8) instead of the dinitro compound (A-1). ..

<Synthesis of polyimide precursor resin (PI-1)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-1 was Mw = 22,100 and Mn = 10,500.
The structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).

<Synthesis of polyimide precursor resin (PI-2)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 8.9 g (46 mmol) of diamine (AA-2) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-2 was Mw = 20,200 and Mn = 9,500.
The structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).

<Synthesis of polyimide precursor resin (PI-3)>
In a flask equipped with a condenser and a stirrer, 14.1 g (47.8 mmol) of 4,4'-biphthalic anhydride was suspended in 74 g of diglyme while removing water. 10.1 g (75 mmol) of diethylene glycol monoethyl ether, 3.25 g (25 mmol) of 2-hydroxyethyl methacrylate and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 12.5 g (45 mmol) of diamine (AA-4) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 8.67 g (188 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-3 was Mw = 22,800 and Mn = 11,000.
The structure of PI-3 is presumed to be the structure represented by the following formula (PI-3). In formula (PI-3), * represents the binding site with the oxygen atom to which R1 binds.

<Synthesis of polyimide precursor resin (PI-4)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 11.4 g (100 mmol) of trifluoro-1-propanol and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 12.5 g (45 mmol) of diamine (AA-4) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-4 was Mw = 21,300 and Mn = 10,200.
The structure of PI-4 is presumed to be the structure represented by the following formula (PI-4).

<Synthesis of polyimide precursor resin (PI-5)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 10.1 g (75 mmol) of diethylene glycol monoethyl ether, 3.25 g (25 mmol) of 2-hydroxyethyl methacrylate and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, 6.54 g (24.75 mmol) of diamine (AA-1), 4,4'-diaminodiphenyl ether ( 4.05 g (20.25 mmol) of Wakayama Seika Co., Ltd. was dissolved in 50 mL of NMP and added dropwise over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-5 was Mw = 24,300 and Mn = 11,200.
The structure of PI-5 is presumed to be the structure represented by the following formula (PI-5). In the formula (PI-5), m and n represent the content ratio (molar ratio) of each repeating unit, m = 5 and n = 4, and * represents the binding site with the oxygen atom to which R1 binds.

<Synthesis of polyimide precursor resin (PI-6)>
In a flask equipped with a condenser and a stirrer, 14.1 g (47.8 mmol) of oxydiphthalic anhydride was suspended in 74 g of diglyme while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 10.8 g (45 mmol) of diamine (AA-5) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 8.67 g (188 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-6 was Mw = 28,100 and Mn = 13,600.
The structure of PI-6 is presumed to be the structure represented by the following formula (PI-6).

<Synthesis of polyimide precursor resin (PI-7)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, 8.32 g (31.5 mmol) of diamine (AA-1), 4,4'-(9-). Fluolenilidene) dianiline (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.70 g (13.5 mmol) was dissolved in 50 mL of NMP and added dropwise over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-7 was Mw = 28,500 and Mn = 12,900.
The structure of PI-7 is presumed to be the structure represented by the following formula (PI-7).

<Synthesis of polyimide precursor resin (PI-8)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. Diethylene glycol monoethyl ether 10.1 g (75 mmol), glycidol (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.85 g (25 mmol), pyridine 16.8 g (132 mmol) were subsequently added, and 5 at a temperature of 60 ° C. Stirred for hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-8 was Mw = 20,800 and Mn = 9,500.
The structure of PI-8 is presumed to be the structure represented by the following formula (PI-8). In formula (PI-8), * represents the binding site with the oxygen atom to which R1 binds.

<Synthesis of polyimide precursor resin (PI-9)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 11.4 g (100 mmol) of trifluoro-1-propanol and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 14.5 g (45 mmol) of diamine (AA-7) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-9 was Mw = 25,400 and Mn = 11,500.
The structure of PI-9 is presumed to be the structure represented by the following formula (PI-9).

<Synthesis of polyimide precursor resin (PI-10)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 74 g of diglyme while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, 7.14 g (27 mmol) of diamine (AA-1), 3.75 g of diamine (AA-6) (AA-6). 18 mmol) was dissolved in 50 mL of NMP and added dropwise over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-10 was Mw = 24,500 and Mn = 10,600.
The structure of PI-10 is presumed to be the structure represented by the following formula (PI-10).

<Synthesis of polyimide precursor resin (PI-11)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 80 g of diglyme while removing water. 19.2 g (100 mmol) of triethylene glycol monoisopropyl ether and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added and 8.15 g (46 mmol) of diamine (AA-3) was dissolved in 50 mL of NMP. It was added by dropping over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-11 was Mw = 22,100 and Mn = 9,800.
The structure of PI-11 is presumed to be the structure represented by the following formula (PI-11).

<Synthesis of polyimide precursor resin (PI-12)>
In a flask equipped with a condenser and a stirrer, 14.8 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 90 g of diglyme while removing water. 11.4 g (100 mmol) of trifluoro-1-propanol and 16.8 g (132 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 20 mL of N-methylpyrrolidone (NMP) was added, and 23.48 g (44 mmol) of diamine (AA-8) was dissolved in 100 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day. The molecular weight of this polyimide precursor PI-12 was Mw = 26,600 and Mn = 12,400.
The structure of PI-12 is presumed to be the structure represented by the following formula (PI-12).

In the polyimide precursor resins PI-1 to PI-12, ^{the ratio of the molar amount of the above G 1} or the above G ² which is a substituent containing an ethylenically unsaturated group, and the organic having 1 to 30 carbon atoms which may contain a hetero atom. molar amount ratio of the G ¹ or the G ² is a group, and an organic group having a polyalkyleneoxy group the ratio of the molar amount of the G ¹ or the G ^2, described in each table below.
In the table below, the description in the column of item 1 is ethylenically unsaturated with respect to the total molar amount of ^{G 1} and G ² in all the repeating units represented by the above formula (1-1) contained in the resin. The ratio of the molar amount of the ^{said G 1} or the said G ² which is a substituent containing a group is shown.
In the table below, the description in the column of item 2 includes heteroatoms with respect to the total molar amount of ^{G 1} and G ² in all the repeating units represented by the above formula (1-1) contained in the resin. The ratio of the molar amount of the ^{G 1} or the G ² which is an organic group having 1 to 30 carbon atoms may be shown.
In the table below, the description in the column of item 3 is a polyalkyleneoxy group with respect to the total molar amount of ^{the above G 1} and the above G ² in all the repeating units represented by the above formula (1-1) contained in the resin. The ratio of the molar amount of the ^{above-mentioned G 1} or the above-mentioned G ² which is an organic group having is shown.
Further, in the table below, the numerical values described in items 1 to 3 are values rounded off to the first decimal place of the numerical values represented by%.

<Synthesis of polyimide precursor (A-1) for comparative example>
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer (polyimide precursor for comparative example (A-). 1)) was obtained. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.
The polyimide precursor (A-1) for comparative example is a resin having no repeating unit represented by the formula (1-1).

<Synthesis of polyimide precursor (A-2) for comparative example>
19.0 g (64) of diphenyl-3,3', 4,4'-tetracarboxylic dianhydride while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. .5 mmol) was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent solution over 1 hour. Viscosity increased while adding 4,4'-diaminodiphenyl ether. Then 6.0 g (188 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor (A-2) for comparative example. The molecular weight of this comparative polyimide precursor (A-2) was Mw = 22,500 and Mn = 9,800.
The polyimide precursor (A-2) for comparative example is a resin having no repeating unit represented by the formula (1-1).

<Synthesis of polyimide precursor (A-3) for comparative example>
In a flask equipped with a condenser and a stirrer, 10.4 g (47.8 mmol) of pyromellitic anhydride was suspended in 74 g of diglyme while removing water. 2-Hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 13.0 g (100 mmol) and pyridine 16.8 g (132 mmol) were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, 1.19 g (4.5 mmol) of diamine (AA-1), 4,4'-diaminodiphenyl ether ( 8.11 g (40.5 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 mL of NMP was added dropwise over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day to obtain a polyimide precursor (A-3) for comparative example. The molecular weight of this comparative polyimide precursor (A-3) was Mw = 22,200 and Mn = 10,300.
It is presumed that the structure of the polyimide precursor (A-3) for Comparative Example is a structure represented by the following formula (A-3). In formula (A-3), the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
The polyimide precursor (A-3) for comparative example is a resin in which the content of the repeating unit represented by the formula (1-1) is 10 mol%.

<Synthesis of polyimide precursor (A-4) for comparative example>
In a flask equipped with a condenser and a stirrer, 9.37 g (47.8 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was suspended in 74 g of diglyme while removing water. .. 2-Hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 13.0 g (100 mmol) and pyridine 16.8 g (132 mmol) were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 5 hours. The mixture was then cooled to −20 ° C. and then 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) was dissolved in 50 mL of NMP. It was added by dropping over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 3 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day to obtain a polyimide precursor (A-4) for comparative example. The molecular weight of this comparative polyimide precursor (A-4) was Mw = 20,600 and Mn = 9,700.
The polyimide precursor (A-4) for comparative example is a resin containing no repeating unit represented by the formula (1-1).
The structure of the polyimide precursor (A-4) for comparative examples is presumed to be the structure represented by the following formula (A-4).

<Examples and Comparative Examples>
In each example, the components shown in Table 2 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition. The obtained curable resin composition and the comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
In Table 2, the numerical value in the column of "parts by mass" indicates the content (parts by mass) of each component.
In Table 2, for example, in the description of "PI-1 / PI-2" in the "Type" column and "16/16" in the "Mass part" column, PI-1 is 16 parts by mass and PI-2. Is shown to have been used for each of the 16 parts.
Further, in Table 2, the description of "-" indicates that the corresponding component is not contained.

Details of each component listed in Table 2 are as follows.

[Specific resin or comparative resin]
-PI-1 to PI-10: Polyimide precursor resins (PI-1) to (PI-10) synthesized above.
-A-1 to A-3: Comparative polyimide precursors (A-1) to (A-3) synthesized above.

〔solvent〕
-DMSO: dimethyl sulfoxide-GBL: γ-butyrolactone-ethyl lactate-NMP: N-methylpyrrolidone In Table 2, DMSO / GBL is described as DMSO and GBL in the ratio of DMSO: GBL = 20: 80 (mass ratio). It shows that they were mixed and used.
In Table 2, the description of NMP / ethyl lactate indicates that NMP and ethyl lactate were mixed and used in a ratio of NMP: ethyl lactate = 80:20 (mass ratio).

[Photopolymerization initiator (photosensitive agent)]
・ OXE-01: IRGACURE OXE 01 (manufactured by BASF)
OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compound]
-SR-209: SR-209 (manufactured by Sartmer)
-SR-231: SR-231 (manufactured by Sartmer)
-SR-239: SR-239 (manufactured by Sartmer)
-ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura 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 following structural formula, Et represents an ethyl group.

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

[Onium salt or thermobase generator]
-I-1: A compound having the following structure

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

<Evaluation>
[Evaluation of film strength (break elongation)]
The curable resin composition or the comparative composition prepared in each Example and each Comparative Example was applied onto a silicon wafer by a spin coating method to form a resin layer.
The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. The obtained curable resin composition layer was entirely exposed to an exposure energy of ^{500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C). After the above exposure, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing conditions" in Table 2, heating was performed for 3 hours. The cured resin composition layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation rate of the obtained test piece in the longitudinal direction was adjusted to JIS-K6251 using a tensile tester (Tensilon) in an environment with a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity). Measured according to. The measurement was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece was broken in each of the 5 measurements was used as an index value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2. It can be said that the larger the index value, the better the film strength of the cured film.
-Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was 50% or more and less than 55%.
D: The above index value was less than 50%.

[Evaluation of chemical resistance]
Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied on a silicon wafer by a spin coating method 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. ^{The curable resin composition layer on the silicon wafer was entirely exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to nitrogen. The cured layer (resin layer) of the curable resin composition layer is heated at a heating rate of 10 ° C./min in an atmosphere at the temperature shown in the “Curing conditions” column of Table 2 for 180 minutes. Got
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: Mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the resin layer in the chemical solution at 75 ° C. for 15 minutes before and after immersion. The dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2. It can be said that the lower the dissolution rate, the better the chemical resistance.
-Evaluation criteria-
A The dissolution rate was less than 200 nm / min.
B The dissolution rate was 200 nm / min or more and less than 300 nm / min.
C The dissolution rate was 300 nm / min or more and less than 400 nm / min.
D The dissolution rate was 400 nm / min or more.

[Ring closure rate]
Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a silicon wafer by a spin coating method, respectively. The silicon wafer after the above application was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform film thickness of 10 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was fully exposed using a stepper (Nikon NSR 2005 i9C). The exposure was performed by i-line, and the exposure was performed at a wavelength of 365 nm with an exposure energy of ^{400 mJ / cm 2.} After the exposure, negative development was carried out with cyclopentanone for 60 seconds to obtain a resin layer. This resin layer is heated in a nitrogen atmosphere at the temperature shown in the column of "curing conditions" in Table 2 for 3 hours to form a cured film A, and then the cured film A is scraped from a silicon wafer and infrared spectroscopic measurement is performed. IR measurement) was performed.
Further, using each curable resin composition or comparative composition prepared in each Example and Comparative Example, "heating at the temperature described in the" curing conditions "column of Table 2 for 3 hours" was performed at "350 ° C." A cured film B was prepared by the same method as that of the cured film A except that the temperature was changed to "heating for 3 hours". The cured film B was also scraped from the silicon wafer and IR measurement was performed.
From the value of the area of the peak corresponding to 1778cm ^-1 in the IR measurement of the cured film A the area of the peak corresponding to 1778cm ^-1 in the IR measurement of the (peak area A) and the cured film B (peak area B), the following equation The ring closure rate was calculated and evaluated according to the following evaluation criteria.
Ring closure rate (%) = peak area A / peak area B x 100
-Evaluation criteria-
A: The ring closure rate was 90% or more.
B: The ring closure rate was 75% or more and less than 90%.
C: The ring closure rate was 50% or more and less than 75%.
D: The ring closure rate was less than 50%.

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.
The comparative compositions according to Comparative Examples 1 to 4 do not contain a specific resin. It can be seen that the comparative compositions according to Comparative Examples 1 to 4 are inferior in chemical resistance.

<Example 101>
The curable resin composition according to Example 1 was spun and applied to the surface of the thin copper layer of the resin base material having the thin copper layer formed on the surface so as to have a film thickness of 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 Corporation). The exposure was carried out through a mask of a square pattern (square pattern of 100 μm each in length and width, number of repetitions of 10) at a wavelength of 365 nm and ^{an exposure amount of 400 mJ / cm 2} to prepare a square remaining pattern. After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the “Curing conditions” column of Example 1 in Table 2, the temperature was heated for 3 hours at this temperature. An interlayer insulating film for the rewiring layer was formed. The interlayer insulating film for the rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

Contains a resin containing a repeating unit represented by the formula (1-1) and a photosensitizer.
The resin contains 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.
Curable resin composition;

In formula (1-1), X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in X 1 are aromatic hydrocarbons. It is a hydrogen group, Y 1 represents an n + divalent group containing an aromatic hydrocarbon group, A 1 represents a group containing a polymerizable group, and G 1 and G 2 are independent hydrogen atoms or substituents, respectively. Represents, and n represents an integer of 1 or more.
The G 1 or the substituent containing an ethylenically unsaturated group with respect to the total molar amount of the G 1 and the G 2 in all the repeating units represented by the formula (1-1) contained in the resin. The curable resin composition according to claim 1, wherein the proportion of the molar amount of G 2 is 0 to 30%.
An organic group having 1 to 30 carbon atoms which may contain a heteroatom with respect to the total molar amount of the G 1 and the G 2 in all the repeating units represented by the formula (1-1) contained in the resin. The curable resin composition according to claim 1 or 2, wherein the ratio of the molar amount of the G 1 or the G 2 is 20 to 100%.
The G 1 or the organic group having a polyalkyleneoxy group with respect to the total molar amount of the G 1 and the G 2 in all the repeating units represented by the formula (1-1) contained in the resin. The curable resin composition according to any one of claims 1 to 3, wherein the ratio of the molar amount of G 2 is 20 to 100%.
The X 1 contains at least one structure selected from the group consisting of the structures represented by the following formulas (A-1) to (A-5), and the Y 1 is the following formula (A2-). 1) The curable resin composition according to any one of claims 1 to 4, which comprises at least one structure selected from the group consisting of the structures represented by the formulas (A2-5);

In formulas (A-1) to (A-5), RA11 to RA14 , RA21 to RA24 , RA31 to RA38 , RA41 to RA48 and RA51 to RA58 are independently hydrogen atoms. , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA31 and LA41 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene group, two of R A11 ~ R A14, two of R A21 ~ R A24 , 2 of RA31 to RA38 , 2 of RA41 to RA48 , and 2 of RA51 to RA58 are binding sites with the carbonyl group in the formula (1-1). Often, * represents the site of connection with other structures independently;

Wherein (A2-1) ~ (A2-5), R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and R A251 ~ R A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA231 and LA241 are independently single-bonded, carbonyl group, sulfonyl group and divalent, respectively. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene group, at least one of R A211 ~ R A214, at least one of R a 221 ~ R A224 one, at least one of R A231 ~ R A238, at least one of R a 241 ~ R A248, and, at least one of the formulas of R A251 ~ R A258 (1-1) in the a 1 of It may be a binding site, and each independently represents a binding site with another structure.
The curable resin composition according to any one of claims 1 to 5, wherein A 1 contains a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group as the polymerizable group.
The curable resin composition according to any one of claims 1 to 6, wherein the photosensitizer is a photopolymerization initiator.
The curable resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.
A cured film obtained by curing the curable resin composition according to any one of claims 1 to 8.
A laminate having two or more layers of the cured film according to claim 9, and having a metal layer between any of the cured films.
A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 8 to a substrate to form a film.
The method for producing a cured film according to claim 11, which comprises a step of heating the film at 50 to 450 ° C.
A semiconductor device having the cured film according to claim 9 or the laminate according to claim 10.
A resin containing 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.

In the formula (1-1), X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and the bonding sites with the four carbonyl groups in the formula (1-1) in X 1 are all aromatic. Group hydrocarbon groups, Y 1 represents an n + divalent group containing an aromatic hydrocarbon group, A 1 represents a group containing a polymerizable group, and G 1 and G 2 are independent hydrogen atoms or groups. It represents a substituent and n represents an integer of 1 or more.
The resin according to claim 14, which has an acid value of 0 to 2.0 mmol / g.
The method for producing a resin according to claim 14 or 15.
A compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group is reacted with a group capable of forming a bond with the reactive group and a compound B having a polymerizable group. After the compound A and the compound B are bonded to each other to obtain a compound C, the nitro group in the compound C is reduced to obtain a diamine having an aromatic hydrocarbon group, and
Production of a Resin comprising a step of reacting the diamine with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the tetravalent carboxylic acid compound. Method.