WO2021107024A1

WO2021107024A1 - Curable resin composition, cured film, layered product, method for producing cured film, semiconductor device, and resin

Info

Publication number: WO2021107024A1
Application number: PCT/JP2020/044050
Authority: WO
Inventors: 敦靖野崎
Original assignee: 富士フイルム株式会社
Priority date: 2019-11-27
Filing date: 2020-11-26
Publication date: 2021-06-03
Also published as: TW202130701A; JPWO2021107024A1; JP2023153860A; JP7319387B2; CN114730132A; KR20220092913A

Abstract

Provided are: a curable resin composition comprising a resin having at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1) and repeating units represented by formula (1-2) and a polymerization initiator; a cured film obtained by curing the curable resin composition; a layered product including the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the layered product. Also provided is a novel resin having a specific structure.

Description

Curable resin composition, cured film, laminate, method for manufacturing cured film, semiconductor device, and 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, and a resin.

Polyimide has excellent heat resistance and insulation properties, so it is applied to various applications. 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, the polyimide may be used in the form of a curable resin composition containing polyimide, or 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, it is expected that the curable resin composition containing polyimide or a polyimide precursor will be applied more and more in industry. ing.

For example, Patent Document 1 describes a photosensitive resin composition containing a polyamic acid having a specific structure, a photopolymerizable compound, and a photopolymerization initiator.

Special Table 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.
Moreover, another embodiment of the present invention aims to provide a novel resin.

Hereinafter, examples of typical embodiments of the present invention will be described.
<1> A resin having at least one repeating unit selected from the group consisting of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (1-2), and a resin. ,
Including polymerization initiator,
Curable resin composition;

In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds, and L ¹¹ represents a divalent linking group containing a polymerizable group;
In formula (1-2), R ²¹ is a tetravalent group having a plurality of amide bonds, L ²¹ represents a divalent group containing a polymerizable group, and R ²² and R ²³ are independent hydrogen atoms. Or represents a monovalent organic group.
<2> The resin has a repeating unit represented by the following formula (2-1) as a repeating unit represented by the above formula (1-1), or is represented by the above formula (1-2). The curable resin composition according to <1>, which has a repeating unit represented by the following formula (2-2) as a repeating unit;

In formula (2-1), X ¹ and X ² are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms, cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. A group is represented, Y ¹ ^{represents an organic group having 1 to 30 carbon atoms, Q 1} represents an organic group having 1 to 30 carbon atoms, and A ¹ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy. Represents a group containing at least one group selected from the group consisting of groups, A ² represents a group containing a polymerizable group, represents a group containing a polymerizable group, and R ¹ and R ² are independent of each other. Represents a hydrogen atom or a monovalent organic group, where n1 and n2 each independently represent an integer greater than or equal to 1.
In formula (2-2), X ³ and X ⁴ are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y ² ^{represents an organic group having 1 to 30 carbon atoms, Q 2} represents an organic group having 1 to 30 carbon atoms, and A ³ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A ⁴ represents a group containing a polymerizable group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. , G ¹ and G ² each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer of 1 or more.
^{<3> X 1} and X ² in the above formula (2-1) are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms, and X ³ and X ^{4 in the above formula (2-2).} The curable resin composition according to <2>, wherein each is an aromatic hydrocarbon group having 6 to 30 carbon atoms independently.
^{<4> Y 1} in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and Y ² in the above formula (2-2) is a group containing an aromatic hydrocarbon group. The curable resin composition according to 2> or <3>.
^{<5> Q 1} in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and Q ² in the above formula (2-2) is a group containing an aromatic hydrocarbon group. The curable resin composition according to any one of 2> to <4>.
<6> The curable resin composition according to any one of <1> to <5>, further comprising a polymerizable compound.
<7> The curable resin composition according to <6>, further comprising a polyfunctional polymerizable compound as the above-mentioned polymerizable compound.
<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> Includes at least one selected from the group consisting of the repeating unit represented by the formula (2-1) and the repeating unit represented by the formula (2-2).
resin.

In formula (2-1), X ¹ and X ² are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y ¹ ^{represents an organic group having 1 to 30 carbon atoms, Q 1} represents an organic group having 1 to 30 carbon atoms, and A ¹ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A ² represents a group containing a polymerizable group, and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group. , N1 and n2 each independently represent an integer greater than or equal to 1.
In formula (2-2), X ³ and X ⁴ are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y ² ^{represents an organic group having 1 to 30 carbon atoms, Q 2} represents an organic group having 1 to 30 carbon atoms, and A ³ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A ⁴ represents a group containing a polymerizable group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. , G ¹ and G ² each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer of 1 or more.

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 is 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).
In the present specification, when simply referring to "aliphatic group", "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl group", "alkylene group", etc., unless otherwise specified, these are used. The group may have at least one of a branched structure and a cyclic structure. 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.
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 "methacrylic", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", 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 Toso Co., Ltd.) 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 Toso Co., Ltd.). 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 shall be performed by using 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 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., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
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”) has a repeating unit represented by the following formula (1-1) and the following formula (1-2). A resin having at least one repeating unit selected from the group consisting of the represented repeating units, and a polymerization initiator are included.
Hereinafter, a resin having at least one repeating unit selected from the group consisting of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (1-2) is referred to as ". Also called "specific resin".

In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds, and L ¹¹ represents a divalent linking group containing a polymerizable group;
In formula (1-2), R ²¹ is a tetravalent group having a plurality of amide bonds, L ²¹ represents a divalent group containing a polymerizable group, and R ²² and R ²³ are independent hydrogen atoms. Or represents a monovalent organic group.
In the present specification, the amide bond refers to a structure represented by (-C (= O) NR-). The R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and has a hydrogen atom and 1 carbon number. It is more preferably an alkyl group of to 4 or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.
In the present specification, when it is simply described as "ester bond (-C (= O) O-)", "urethane bond (-OC (= O) NR-)", "amide bond", etc., these The orientation of the bond is not limited. R in the urethane bond (-OC (= O) NR-) is synonymous with R in the amide bond described above, and the preferred embodiment is also the same.

The curable resin composition of the present invention 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.
Further, in the present invention, the repeating unit means the smallest of the constituent units constituting the resin by being repeatedly connected. That is, for example, a resin having a structural unit in which two repeating units represented by the formula (1-2) are bonded has one repeating unit in which two repeating units represented by the formula (1-2) are bonded. It is not a resin, but a resin having two repeating units represented by the formula (1-2).

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 or polyimide precursor conventionally used, the specific resin contains a plurality of amide bonds in ^{R 11} or R ^{21 in the formula (1-1) or the formula (1-2).} Moreover, L ¹¹ or L ²¹ contains a polymerizable group.
Since the amide bond has a high hydrogen bond property, it is considered that the resin contains the above-mentioned plurality of amide bonds, so that an interaction occurs between the resins or within the resin. In the cured film after curing, it is presumed that a dense network-like structure is formed by ^{the above-mentioned interaction and cross-linking by polymerization of the polymerizable group contained in L 11} or L ²¹ close to the above-mentioned amide bond. To. It is considered that chemicals are less likely to permeate into the cured film in which such a dense network-like structure is formed. As described above, according to the curable resin composition of the present invention, it is presumed that a cured film having excellent chemical resistance with suppressed penetration of chemicals can be obtained.
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, since the specific resin has a polymerizable group having high solvent solubility in L 11} or L ²¹ in the formula (1-1) or the formula (1-2), the developing solution permeates the composition before polymerization. Since the properties are improved, it is presumed that a composition film (photosensitive film) having excellent developability can be easily obtained.

Here, in Patent Document 1, at least one kind of repeating unit selected from the group consisting of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2) is used. There is no description or suggestion about the resin to have. Further, the curable resin composition in Patent Document 1 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 has at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2).
The specific resin has at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2) in the side chain. Although it may be used, it is preferable to have the repeating unit 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)]
-R ¹¹ -
In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds.
The ^{amide bond contained in R 11} may be contained in the main chain of the specific resin or in the side chain of the specific resin, but from the viewpoint of chemical resistance, it is contained in the main chain of the specific resin. Is preferable.
The number of amide bonds in R ¹¹ may be 2 or more, preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and 2 or 3. It is particularly preferable to have, and most preferably 2.
R ¹¹ may be a tetravalent group, but preferably contains at least one group selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and two or more amide bonds. ..
From the viewpoint of developability, R ¹¹ is preferably a group containing an aromatic ring hydrocarbon group.
Further, from the viewpoint of chemical resistance, R ¹¹ is preferably a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group and a (meth) acryloxy group are preferable. A group, a maleimide 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 R ¹¹ is preferably 1 or more, more preferably 1 to 15, further preferably 1 to 10, and 1 to 5. Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
From the viewpoint of developer solubility, R ¹¹ preferably has at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkyleneoxy group as a substituent.
As these substituents, a group represented by the formula (P-4) described later is preferable.

<< Formula (R-1) >>
Among these, R ¹¹ is preferably a group represented by the following formula (R-1).

In formula (R-1), X ¹ and X ² are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. ^{L 1} and L ² independently represent a single bond or a divalent linking group, R ¹ and R ² independently represent a hydrogen atom or a hydrocarbon group, and L ³ represents a divalent link. Each represents a group, * represents a bonding site with one of the two imide structures in the formula (1-1), and # represents a bonding site with the other of the above imide structures, respectively.

<<< X ¹ and X ² >>>
In the formula (R-1), ^{each of X 1} and X ² is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aliphatic ring group having 3 to 30 carbon atoms, respectively.
As the aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 10 carbon atoms is further preferable, and a hydrogen atom from a benzene ring. A structure excluding three is more preferable.
As the aliphatic ring group having 3 to 30 carbon atoms, an aliphatic ring group having 4 to 20 carbon atoms is more preferable, an aliphatic ring group having 6 to 10 carbon atoms is more preferable, and an aliphatic ring group having a 6-membered ring structure is more preferable. A structure in which three hydrogen atoms are removed from the ring structure is more preferable.
The aliphatic ring group may be a saturated aliphatic ring group or an unsaturated aliphatic ring group, but is preferably a saturated aliphatic ring group.
The aliphatic ring group may be an aliphatic hydrocarbon ring group or an aliphatic heterocyclic group, but is preferably an aliphatic hydrocarbon ring group.
Among these, the saturated aliphatic hydrocarbon group is preferable as the aliphatic ring group.
In an aromatic hydrocarbon group or an aliphatic ring group which is ^{X 1} or X ² ^{, two * in X 1} and two #s in X ² are adjacent positions in the aromatic hydrocarbon group or an aliphatic ring group. It is preferred to be present.
In the present specification, when two binding sites are present at adjacent positions in a ring structure, 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.

The above-mentioned X ¹ and X ² 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.

<<< L ¹ and L ² >>>
In formula (R-1), L ¹ and L ² are independently single bonds, hydrocarbon groups, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- or a group in which two or more of these are bonded is preferable, and a single bond is more preferable. Preferred examples of the above-mentioned "group in which two or more of these are bonded" include a urea group and the like.
The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aromatic hydrocarbon group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and has 1 to 10 carbon atoms. More preferably, it is a saturated aliphatic hydrocarbon group of the above, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
Further, ^{the hydrocarbon group in L 1} and L ² may have a group containing a polymerizable group as a substituent. The polymerizable group include polymerizable groups in R ¹¹ described above.
From the viewpoint of developer solubility, the ^{hydrocarbon groups in L 1} and L ² are substituted with a group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkyleneoxy group. It is preferable to have it as a group. As these substituents, a group represented by the formula (P-4) described later is preferable.

In the formula (R-1), R ¹ and R ² independently represent a hydrogen atom or a hydrocarbon group, a hydrogen atom, an alkyl group or an aromatic hydrocarbon group is more preferable, and a hydrogen atom or an alkyl group is further preferable. , Hydrogen atom is particularly preferable.

<<< L ³ >>>
In formula (R-1), L ³ is a hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , or these are 2. The group bonded as described above is preferable, and a hydrocarbon group or at least one hydrocarbon group and -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , And a group to which at least one structure selected from the group consisting of urea groups is bonded is preferable. The above ^RN is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and has 1 to 10 carbon atoms. More preferably, it is a saturated aliphatic hydrocarbon group of the above, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
Further, the hydrocarbon group of L ³ are polymerizable groups, aliphatic hydrocarbon groups, and, a group containing at least one group selected from the group consisting of polyalkyleneoxy group may have a substituent .. The polymerizable group include polymerizable groups in R ¹¹ described above.
From the viewpoint of chemical resistance of the obtained cured film, it is preferable to have a group containing at least a polymerizable group as a substituent.
From the viewpoint of developer solubility, it is preferable to have a group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkyleneoxy group as a substituent. As these substituents, a group represented by the formula (P-4) described later is preferable.
As the ^{L 3,} preferably a group represented by the following formula (L-1).

In the formula (L-1), Y ¹ represents an organic group having 1 to 30 carbon atoms, and A ¹ is at least one selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing a species group, n1 represents an integer of 1 or more, * represents ^{the bonding site with the nitrogen atom to which R 1} in the formula (R-1) is bonded, and # represents the bonding site with the nitrogen atom to which R 1 is bonded, and # represents the bonding site with the nitrogen atom in the formula (R-1). It represents the bonding site with the nitrogen atom to which ^{R 2 is bonded.}

In formula (L-1), Y ¹ is a hydrocarbon group, or at least one hydrocarbon group, and -O-, -C (= O)-, -S-, -S (= O) _2- , It is preferably a group in which at least one structure selected from the group consisting of -NR ^N- is bonded, and a hydrocarbon group or a structure in which at least one hydrocarbon group and an amide bond are bonded. preferable.

Further, Y ¹ is preferably a group represented by the following formula (Y-1).

In formula (Y-1), ^RY1 , ^RY2, and ^RY3 independently represent organic groups having 1 to 30 carbon atoms, and Z ¹ and Z ² independently represent amide bonds, a and b. are each independently an integer of 0 or more, of ^R ^{Y1, R Y2} and ^{R Y3} is present in formula (Y1), at least one binding site to ^{a 1} in the formula (L-1) Represents.

In the formula (Y-1), ^RY1 , ^RY2, and ^RY3 are each independently preferably an aliphatic hydrocarbon group or a group containing an aromatic hydrocarbon group, and each contains an aromatic hydrocarbon group. It is preferably a group.
As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable, and an aliphatic hydrocarbon group having 2 to 20 carbon atoms is more 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 an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable. More preferably, an aromatic hydrocarbon group having 6 carbon atoms is particularly preferable.
^Further, each of R ^{Y1, R Y2} and ^{R Y3} independently is preferably a structure represented by any one of the following formulas (Y1-1) ~ Formula (Y1-4), Formula (Y1-3) or The structure represented by the formula (Y1-4) is more preferable, and the structure represented by the formula (Y1-3) is more preferable.
Bonds in the formula (Y1-1) ~ (Y1-4), * respectively, the binding site with another structure, each #, a binding site or a hydrogen atom and ^{A 1} in formula (L-1) Represents a part.

Wherein (Y1-1) or Formula ^{(Y1-2), L Y1} and ^{L Y2} each independently represent an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 4 carbon atoms More preferably, a methylene group is further preferable.
Wherein (Y1-3) or Formula ^{(Y1-4), L Y4} each independently represent a single bond or a divalent hydrocarbon group, preferably a single bond. As the divalent hydrocarbon group, an alkylene group is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
Wherein ^{(Y1-4), L Y3} is a single bond or an aliphatic hydrocarbon group which 1 carbon atoms which may be ~ 10 substituted by fluorine atoms, -O -, - C (= O) -, - It is preferably S-, -S (= O) _2- , -NHC (= O)-, or a group in which two or more of these are combined, and is a single bond or a group having 1 carbon atom which may be substituted with a fluorine atom. It is more preferable that the alkylene group of ~ 3 is -O-, -C (= O)-, -S- or -S (= O) _2- _{, and -CH 2-} , -O-, -S-, More preferably, it is a divalent group selected from the group consisting of -S (= O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2-.
In the formula (Y1-3) or the formula (Y1-4), n independently represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

In the formula (Y-1), the ^{amide bond in Z 1} and Z ² is independently the same as the ^{amide bond in R 11} described above, and the preferred embodiment is also the same.
Further, the direction of the amide bond in ^{Z 1} and Z ^{2 is not particularly limited.}

In the formula (Y-1), a and b each independently represent an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and 0 or 1. It is more preferably present, and 0 is particularly preferable.

In formula (L-1), A ¹ represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group.
As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group and a (meth) acryloxy group are preferable. A group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol 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.
When A ¹ is a group ^{containing a polymerizable group, the number of polymerizable groups contained in A 1} is 1 or more, preferably 1 to 15, and more preferably 1 to 10. Preferably, the number is more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.
A ^{preferred embodiment when A 1} is a group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkyleneoxy group is L ^{3 in the above formula (R-1).} As described as a substituent of.

When A ¹ contains a polymerizable group, it is preferably a group represented by the following formula (P-1).

In formula (P-1), L ¹ represents a single bond or an m + 1 valent linking group, A ² represents a polymerizable group, m represents an integer of 1 or more, and * represents a binding site with ^{Y 1.} ..
In formula (P-1), L ¹ is a single bond or a hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , Alternatively, a group in which two or more of these are bonded is preferable, and a single bond, or a hydrocarbon group, -O-, -C (= O)-, -NR ^N- , or a group in which two or more of these are bonded is more preferable. .. Examples of the above-mentioned "group in which two or more of these are bonded" include a urea group and the like.
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.
As ^{the hydrocarbon group in L 1} , a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferable, and the group has a carbon 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, L ² is a hydrocarbon group or a hydrocarbon group, and -O-, -C (= O)-, -S-, -S ( = O) _2- , -NR ^N- , carbonate bond, urea group, or a group in which two or more of these are bonded, and Z ¹ is an ether bond, ester bond, urethane bond, urea bond, carbonate bond, or amide. It represents a 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, and more preferably a hydrocarbon 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.
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 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.
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.
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, or an amide bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
Wherein (P-3), * represents a bonding site with ^{Y 1.}

From the viewpoint of chemical resistance ^{, the distance between the polymerizable group contained in A 1} and the main chain of the specific resin is preferably 0 to 15, and more preferably 0 to 10.
Here, ^{the distance between the polymerizable group contained in A 1} and the main chain of the specific resin is the smallest of the number of atoms contained between the atom contained in the main chain of polyimide and the polymerizable group. Say a number. For example, in the resin represented by the formula (PI-1) in the examples described later, the distance between the methacryloxy group and the main chain is 4.
That is, when the polyimide has a ring structure inside the main chain, the "atoms contained in the main chain of the above-mentioned polyimide" include the ring members of the ring structure.
Further, when A ¹ contains a plurality of polymerizable groups, of polymerizable groups contained in A ^1, and a polymerizable group closest to the main chain, that the distance between the main chain of the polyimide is 0-15 It is preferably 0 to 10, and more preferably 0 to 10. Furthermore, it if A ¹ contains a plurality of polymerizable groups, and all of the polymerizable groups contained in A ^1, still more preferably the distance between the main chain of the polyimide is 0-15, 0-10 Is particularly preferable.

When A ¹ is a group containing at least one selected from the group consisting of an aliphatic hydrocarbon group and a polyalkyleneoxy group, A ¹ is preferably a group represented by the following formula P-4. ..

In formula (P-4), L ⁴ represents a single bond or an m + 1 valent linking group, A ⁴ represents an aliphatic hydrocarbon group, a polyalkyleneoxy group or a group represented by a bond thereof, and m is 1. represents an integer greater than or equal, * represents a bonding site with Y ^1.
In formula (P-4), L ⁴ is a single bond or a hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , Alternatively, a group in which two or more of these are bonded is preferable, an ester bond, an amide bond, a urea bond, or a urethane bond is more preferable, and an ester bond is further preferable.
Wherein (P-4), the aliphatic hydrocarbon group for A ^4, alkyl group, more preferably a linear alkyl group or branched alkyl group, branched alkyl group is more preferable. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 4 to 30, and more preferably 6 to 20.
Wherein (P-4), examples of the group include a polyalkyleneoxy group in A ^4, include the same groups as groups containing polyalkyleneoxy group in R ²² described below, preferred embodiment is also the same.
Wherein ^(P-4), A 4 is a group containing a polymerizable group described above as a substituent, or may have other known substituents.
In the formula (P-4), m represents an integer of 1 or more, an integer of 1 to 10 is preferable, an integer of 1 to 4 is more preferable, 1 or 2 is further preferable, and 1 is particularly preferable.

In the formula (L-1), n1 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 n1 is an integer of 2 or more, it may be respectively the same n1 pieces of A ^1, may be different.

<<< R ¹ and R ² >>>
In the formula (R-1), R ¹ and R ² independently represent a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferable, and the hydrogen atom has 1 to 4 carbon atoms. Alkyl groups or aromatic hydrocarbon groups having 6 to 12 carbon atoms are more preferable, and hydrogen atoms are even more preferable.

-L ¹¹ -
In formula (1-1), L ¹¹ represents a divalent linking group containing a polymerizable group.
The polymerizable group in L ^11, group containing an ethylenically unsaturated bond, a cyclic ether group, a group containing a methylol group or an alkoxymethyl group are preferred, a vinyl group, (meth) allyl group, (meth) acrylamide group, ( More preferably, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group More preferred.
The number of polymerizable groups contained in L ¹¹ is preferably 1 or more, more preferably 1 to 15, further preferably 1 to 10, and 1 to 5. Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
From the viewpoint of developability, L ¹¹ is preferably a group containing an aromatic hydrocarbon group, more preferably a group containing an aromatic hydrocarbon group having 6 to 30 carbon atoms, and has a benzene ring structure. , Or a group containing a naphthalene ring structure is more preferable, and a group containing a benzene ring structure is particularly preferable.

<< Formula (L-2) >>
Among these, L ¹¹ is preferably a group represented by the following formula (L-2).

In the formula (L-2), Q ¹ represents an organic group having 1 to 30 carbon atoms, A ² represents a group containing a polymerizable group, n 2 represents an integer of 1 or more, and * represents another structure. Represents a binding site.

<< Q ¹ >>
Q ¹ is preferably an n2 + divalent group containing an aromatic hydrocarbon group.
Aromatic hydrocarbon group in Q 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 is obtained by removing the hydrogen atom of, and it is particularly preferable that the group is obtained by removing 3 or more hydrogen atoms from the benzene ring.
Wherein (L-2), in Q ^1, 2 single * the binding site of according to formula (L-2) 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 Q ^1, it is preferable to directly bond.
Further, in the formula (L-2), it is preferable that the binding site with ^{A 2} ^{in Q 1} is an aromatic hydrocarbon group. That is, it is preferable that A ² is directly bonded to the aromatic hydrocarbon ring structure contained ^{in Q 1.}

Q 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 Q1. 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 2} in the formula (L-2) It may be a binding site, and each independently represents a binding site with another structure.

Among these, from the viewpoint of solvent solubility, ^{Q 1} is preferably a structure represented by any of formulas (A2-1) ~ formula (A2-4), is represented by the formula (A2-1) It is more preferable to include a structure such as

Wherein ^{^{(A2-1), R A211 ~ R}} A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, 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.
Halogen atom in the halogenated alkyl group in the R ^{A211 ~} R ^A214, or, as the halogen atom, fluorine atom, chlorine atom, bromine atom, and an iodine atom, a chlorine atom or a bromine atom.
Further, among the ^R A211 ^{~ R A214,} is preferably a binding site with ^{A 2} in at least Exemplary ethynylphenylbiadamantane derivatives ^(L-2), it is more preferable ^{R A213} is a bond site to the ^{A 2} ..

Wherein ^(A2-2), each of ^R A221 ^~ R ^A224, have the same meanings as ^{^R} A211 ^~ ^R ^A214 in formula (A2-1), preferable embodiments thereof are also the same.
Further, among the ^R A211 ^{~ R A214,} it is preferably a binding site with ^{A 2} in at least Exemplary ethynylphenylbiadamantane derivatives (L-2), 1 or 2 is a binding site between the ^{A 2} More preferred.

Wherein ^(A2-3), each of ^R A231 ^~ R ^A238, have the same meanings as ^{^R} A211 ^~ ^R ^A214 in formula (A2-1), preferable embodiments thereof are also the same.
In the formula (A2-3), ^LA231 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- , urea group, heterocyclic group, or halogenated alkylene group having 1 to 6 carbon atoms is preferably represented, and a single bond, saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or It preferably represents a heterocyclic group, more preferably a single bond or —O—. The ^RN is as described above, and the preferred embodiment is also the same.
Further, among the ^{^R} A231 ^~ ^R ^A238, it is preferably a binding site with ^{A 2} in at least Exemplary ethynylphenylbiadamantane derivatives (L-2), 1 or 2 is a binding site between the ^{A 2} more ^preferably, bract one of R A231 ^{~ R ^A234,} it is more preferably one of ^R A235 ^~ R ^A238 is a bond site between the ^{a 2.}

Wherein ^(A2-4), each of ^R A241 ^~ R ^A248 and ^{L A 241,} has the same meaning as ^{^R} A231 ^~ ^R ^A238 and ^{L A231} in formula (A2-3), preferable embodiments thereof are also the same.
Further, ^{it is preferable that at least one of the above RA241} to ^RA248 is a binding site with ^{A 2} in the formula (L-2), and one or two are binding sites with the ^{above A 2.} more ^preferably, bract one of R a 241 ^{~ R ^A244,} it is more preferably one of ^R A245 ^~ R ^A248 is a bond site between the ^{a 2.}

Wherein ^{^{(A2-4), R A251 ~ R}} A258 have the same meanings as ^{^R} A211 ^~ ^R ^A214 in formula (A2-1), preferable embodiments thereof are also the same.
Further, ^{it is preferable that at least one of the above RA251} to ^RA258 is a binding site with ^{A 2} in the formula (L-2), and one or two are binding sites with the ^{above A 2.} more ^preferably, bract one of R a 251 ^{~ R ^A254,} it is more preferably one of ^R A255 ^~ R ^A258 is a bond site between the ^{a 2.}

<< A ² >>
In formula (L-2), A ² represents a group containing a polymerizable group.
As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group and a (meth) acryloxy group are preferable. A group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol 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 ² 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 ² is preferably a group represented by the above formula (P-1), and is preferably a group represented by the above formula (P-2) or the above formula (P-3). More preferred.

<< n2 >>
In the formula (L-2), n2 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.
Moreover, if n2 is an integer of 2 or more, it may be a respective n2 amino A ² same or different.

-Equation (2-1)-
When the specific resin has a repeating unit represented by the formula (1-1), the specific resin is a repeating unit represented by the following formula (2-1) as a repeating unit represented by the formula (1-1). It is preferable to have.

In formula (2-1), X ¹ and X ² are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms, cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. A group represents a group, Y ¹ ^{represents an organic group having 1 to 30 carbon atoms, Q 1} represents an organic group having 1 to 30 carbon atoms, and A ¹ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A ² represents a group containing a polymerizable group, and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group. , N1 and n2 each independently represent an integer of 1 or more.

In the above formula ^(2-1), X ^1, X 2, ^{R 1} and ^{R 2} each has the same meaning as ^X ^1, X 2, ^{R 1} and ^{R 2} in the above formula (R-1), preferably The aspect is also the same.
In the above formula (2-1), Y ¹ , A ¹ ^{and n 1 are synonymous with Y 1} , A ¹ and n 1 in the above formula (L-1), respectively, and the preferred embodiments are also the same.
In the formula ^(2-1), respectively Q 1, ^{A 2} and ^{n 2} are the same as ^Q 1, ^{A 2} and ^{n 2} in the above formula (L-2), preferable embodiments thereof are also the same.

[Repeating unit represented by equation (1-2)]
-R ²¹ -
In formula (1-2), R ²¹ ^{has the same meaning as R 11} in formula (1-1), and the preferred embodiment is also the same.

-L ²¹ -
In formula (1-2), L ²¹ ^{has the same meaning as L 11} in formula (1-1), and the preferred embodiment is also the same.

-R ^22, ^{R 23} -
R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that both are monovalent organic groups.
Examples of the monovalent organic group in R ²² and R ²³ include a group containing a polymerizable group or an organic group which may contain a hetero atom, from the viewpoints of chemical resistance, developability and solvent solubility of the specific resin. Therefore, a group containing a polyalkyleneoxy group is preferable.

<< Groups containing polymerizable groups >>
As the ^{polymerizable group contained in the group containing a polymerizable group in R 22} and R ²³ , a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, ( More preferably, (meth) allyl group, (meth) acrylamide group, (meth) acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, methylol group or alkoxymethyl group, (meth) acryloxy group, (meth) acrylamide group. More preferred are groups, epoxy groups, methylol groups or alkoxymethyl groups.
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 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 or a methyl group, and 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. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
In formula (III), * represents a binding site with another structure.

<< 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 an organic group having 2 to 20 carbon atoms which may contain a heteroatom. More preferred.

<<< Polyalkyleneoxy group >>>
Among these, the organic group which may contain the heteroatom is preferably an organic group containing 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. The group to which the propyleneoxy group is bonded is preferable, the polyethyleneoxy group or the polypropyleneoxy group is more preferable, and the 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 containing 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 bonding site with an oxygen atom to which ^{R 22} or R ^{23 in the formula (1-2) 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, a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, ( More preferred are 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, with a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group and a methylol. Groups or alkoxymethyl groups are more preferred.
As the group containing the above-mentioned polymerizable group, the group represented by the above-mentioned formula (P-1) is preferable, and the group represented by the above-mentioned formula (P-2) or the above-mentioned formula (P-3) 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.
The divalent linking group includes a hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , or two or more of these. The group is preferably a hydrocarbon group, —O—, −C (= O) −, −NR ^N− . Alternatively, 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 film strength, 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 a hydrocarbon group substituted with a halogen atom as R ²² or R ²³ , the film strength of the obtained cured film is improved.

<< Other substituents >>
R ²² and R ²³ may be other substituents.
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 hydrocarbon group having a phenolic hydroxy group or an aralkyl group having a phenolic hydroxy group is more preferable. , A phenyl group having a phenolic hydroxy group, or a benzyl group having a phenolic hydroxy group is more preferable.
Further, as the other substituent, a group such as an alkyl group, an aryl group, an alkoxyalkyl group, an aryloxy group, or an alkyl group may be used.

From the viewpoint of film strength and chemical resistance, it contains ethylenically unsaturated bonds with respect to the total molar amount ^{of R 22} and R ^{23 in} the repeating unit represented by the formula (1-2) contained in the specific resin. The ratio of the molar amounts of the substituents R ²² and R ²³ is preferably 0 to 60%, more preferably 0 to 30%.
From the viewpoint of film strength, 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 film strength, chemical resistance, and solvent solubility of the specific resin, the total molar amount ^{of R 22} and R ^{23 in the repeating unit represented by the above formula (1-2) contained in the above resin.} , The ratio of the molar amount of ^{R 22} and R ²³ , which are organic groups having 1 to 30 carbon atoms which may contain a hetero atom, is preferably 20 to 100%.
From the viewpoint of film strength, 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 preferably 80% or less. It is particularly preferable, and most preferably 70% or less.

From the viewpoint of film strength, chemical resistance, and solvent solubility of the specific resin, the total molar amount ^{of R 22} and R ^{23 in the repeating unit represented by the above formula (1-2) contained in the above resin.} , The ratio of the molar amount of the ^{above R 22} and R ²³ , which are organic groups containing a polyalkyleneoxy group, is preferably 20 to 100%.
The organic group containing 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 film strength, 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 preferably 80% or less. It is particularly preferable, and most preferably 70% or less.
From the viewpoint of developer solubility, for example, R ²¹ in the above formula (1-2) is at least one selected from the group consisting of the above-mentioned aliphatic hydrocarbon group and polyalkyleneoxy group. A mode in which a group containing at least the above-mentioned group is used as a substituent and R ²² ^{and R 23} are used as the other substituents described above is also preferably mentioned.
In this case, to the total molar amount of ^{R 22} and ^{R 23} in the repeating unit represented by the above formula (1-2), the ratio of the molar amount of the ^{R 22} and ^{R 23} is another substituent described above, It is also preferably 50 to 100%.

-Equation (2-2)-
When the specific resin has a repeating unit represented by the formula (1-2), the specific resin is a repeating unit represented by the following formula (2-2) as a repeating unit represented by the formula (1-2). It is preferable to have.

In formula (2-2), X ³ and X ⁴ are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y ² ^{represents an organic group having 1 to 30 carbon atoms, Q 2} represents an organic group having 1 to 30 carbon atoms, and A ³ represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A ⁴ represents a group containing a polymerizable group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. , G ¹ and G ² each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer of 1 or more.

In the formula (2-2), X ³ and X ⁴ ^{are synonymous with X 1} and X ² in the above formula (2-1), respectively, and the preferred embodiments are also the same.
In the formula (2-2), R ³ and R ⁴ ^{are synonymous with R 1} and R ² in the above formula (2-1), respectively, and the preferred embodiments are also the same.
In formula (2-2), Y ² , A ³ ^{and n 3 are synonymous with Y 1} , A ¹ and n 1 in the above formula (2-1), respectively, and the preferred embodiments are also the same.
In the formula ^(2-2), each Q 2, ^{A 4} and n4, have the same meanings as ^Q 1, ^{A 2} and n2 in the above formula (2-1), preferable embodiments thereof are also the same.
In formula (2-2), G ¹ and G ² ^{are synonymous with R 23} and R ²² in the above formula (1-2), respectively, and the preferred embodiments are also the same.

Among these, the specific resin has a repeating unit represented by the above formula (2-1) as a repeating unit represented by the above formula (1-1), or is represented by the above formula (1-2). It is preferable to have a repeating unit represented by the above formula (2-2) as the repeating unit to be formed.

From the viewpoint of solvent solubility and developability, X ¹ and X ² in the above formula (2-1) are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms, and the above formula (2-2). ), ^{It is preferable that X 3} and X ⁴ are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms.

From the viewpoint of solvent solubility and developability, Y ¹ in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and Y ² in the above formula (2-2) is an aromatic hydrocarbon. It is preferably a group containing a group.

From the viewpoint of solvent solubility and developability, Q ¹ in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and Q ² in the above formula (2-2) is an aromatic hydrocarbon. It is preferably a group containing a group.

-Content of repeating unit-
The total content of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2) in the specific resin is 50 mol% or more with respect to all the repeating units of the specific resin. It is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the content is not particularly limited, and may be 100 mol% or less.
Further, the total content of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2) in the specific resin is 50% by mass or more with respect to the mass of the specific resin. It is preferably 60% by mass or more, 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.

When the specific resin has a repeating unit represented by the formula (1-1), the content of the repeating unit represented by the formula (1-1) is 50 mol% or more with respect to all the repeating units of the specific resin. It can also be in some form. The content is more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the content is not particularly limited, and may be 100 mol% or less.
When the specific resin has a repeating unit represented by the formula (1-2), the content of the repeating unit represented by the formula (1-2) is 50 mol% or more with respect to all the repeating units of the specific resin. It can also be in some form. The content is more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the content is not particularly limited, and may be 100 mol% or less.

When the specific resin has a repeating unit represented by the formula (1-1), the repeating unit represented by the formula (1-1) may be contained alone, or the formula (1-1) having a different structure may be contained. Two or more types of repeating units represented by may be included. 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.
When the specific resin has a repeating unit represented by the formula (1-2), the repeating unit represented by the formula (1-2) may be contained alone, or the repeating unit having a different structure (1-2) may be contained. Two or more types of repeating units represented by may be included. When the specific resin contains two or more repeating units represented by the formula (1-2) having different structures, the total content of the repeating units represented by the formula (1-2) contained in the specific resin is , It is preferable that the content is within the above range.

When the specific resin has a repeating unit represented by the formula (1-1), the imidization rate (ring closure rate) of the specific resin is preferably 70% or more. The imidization ratio is more preferably 80% or more, and further preferably 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by, for example, the following method.
The infrared absorption spectrum of the specific resin is measured, and the peak intensity P1 near ^{1377 cm -1,} which is the absorption peak derived from the imide structure, is obtained. Next, the polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of the specific resin can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[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 (1-2) shall not correspond to the repeating unit represented by the following formula (1).
When the specific resin has 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.
The repeating unit represented by the above formula (1) is a repeating unit in which the number of amide bonds contained ^{in R 115} ^{is 1 or less, or R 111} does not have a polymerizable 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 independently represent a hydrogen atom or a monovalent organic group, and are preferably monovalent organic groups.
Further, ^{it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group.
The ^{monovalent organic group in R 113} and R ¹¹⁴ ^{is a group containing a polymerizable group in R 22} and R ²³ in the above formula (1-2), an organic group which may contain a hetero atom, or an organic group. Other substituents are also preferably mentioned.

In the formula (1), the R ¹¹⁵ may have the same structure as the ^{R 21} in the above formula (1-2). When R ¹¹⁵ ^{in the formula (1) has the same structure as R 21} in the above formula (1-2) ^{, R 111} in the formula (1) has a structure not containing a polymerizable group.
Further, R ¹¹⁵ is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO−, —S—, —SO. _2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO _2- _{, -CH 2-} , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2-, -O-, -CO.} It is more preferably a divalent group selected from the group consisting of-, -S- and SO _2-.
In formulas (5) and (6), * represents a binding site with another structure, respectively.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride 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 represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1), and preferred ranges are also the same.

Specific examples of the tetracarboxylic dianhydride include 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 dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , 7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,5-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-phenanthenetetracarboxylic dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethanedianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these Examples thereof include alkyl having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

In the formula (1), the R ¹¹¹ may have the same structure as the ^{L 21} in the above formula (1-2). When R ¹¹¹ ^{in the formula (1) has the same structure as L 21} in the above formula (1-2), the number of amide bonds contained ^{in R 115} in the formula (1) is 1 or less. ..
In the formula (1), R ¹¹¹ may have a structure containing no polymerizable group.
Further, R ¹¹¹ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , and at least one of the urea groups are preferably bonded. ^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 is the same meaning as ^{L A231} in the above formula (A2-3), preferable embodiments thereof are 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.

^{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) ) Etan, 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) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.
Diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598 are also preferably used.

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.

-Repeating unit represented by equation (4)-
The specific resin may further contain a repeating unit represented by the formula (4).
When the specific resin has a repeating unit represented by the following formula (4), the specific resin preferably contains a repeating unit represented by the following formula (4) in the main chain.
However, the repeating unit represented by the above equation (1-1) does not correspond to the repeating unit represented by the equation (4).

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
In formula (4), R ¹³¹ and R ¹³² ^{have the same meaning as R 111} and R ^{115 in} formula (1), respectively, and the preferred embodiments are also the same.

<< Content >>
The total content of the other repeating units in the specific resin is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass with respect to the total mass of the specific resin. The following is more preferable. 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 form that does not substantially contain other repeating units.
In this case, the total content of the other repeating units is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass or less with respect to the total mass of the specific resin. Is more preferable. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The specific resin may contain one other repeating unit alone, or may contain two or more other repeating units having different structures. When the specific resin contains two or more other repeating units having different structures, it is preferable that the total content of all the other repeating units contained in the specific resin is included in the above content range.

-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 a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It may be sealed with. Of these end-capping agents, it is preferable to use monoamines. 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.

〔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).

-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.
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.

[Manufacturing method (Manufacturing method of a specific resin having a repeating unit represented by the formula (1-2))]
When the specific resin has a repeating unit represented by the formula (1-2), the specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.
Further, the method for producing a specific resin having a repeating unit represented by the formula (1-2) preferably includes a step (precursor manufacturing step) of reacting a diamine with a tetravalent carboxylic acid compound or a derivative thereof. ..

-Precursor manufacturing process-
Examples of the diamine used in the precursor production step include diamines represented by the following formula (DA-1).

Wherein ^{(DA-1), L 21} has the same meaning as ^{L 21} in the formula (1-2), preferable embodiments thereof are also the same.
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, in the carboxylic acid dianhydride represented by the formula (DC-1) described later, a compound in which two carboxy groups are esterified among the four carboxy groups after hydrolysis can be mentioned.
It is preferable that ^{R 22} and R ²³ in the above formula (1-2) are introduced by the above esterification.
Further, it is preferable that a 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. A step (diamine production step) may be included in which a compound B having the above-mentioned compound B is reacted to obtain a compound C to which the compound A and the compound B are bonded, and then the nitro group in the compound C is reduced to obtain a diamine.
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 an 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.
Examples of the polymerizable group in compound B include the groups exemplified as the groups contained ^{in L 22 in the above formula (1-2).}

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).

-Carboxylic acid dianhydride manufacturing process-
The method for producing the specific resin is a step of reacting a diamine compound with one carboxylic acid anhydride group and a compound having one carboxy group to obtain a carboxylic acid dianhydride having two or more amide bonds (carboxylic acid). (Dianhydride production step) may be included.
The one carboxy group may be a carboxylic acid halide group.
The details of the above reaction may be determined with reference to a known amidation method.
For example, in the synthesis of the anhydride (MA-1) in the examples described later, the anhydride compound is a compound having AA-1 which is a diamine compound, one carboxylic acid anhydride group, and one carboxylic acid halide group. Merit This is a reaction for reacting with an acid chloride to obtain an anhydride (MA-1) having two amide bonds.
Examples of the obtained carboxylic acid dianhydride include compounds represented by the following formula (DC-1).

In the formula ^{(DC-1), R 21} has the same meaning as ^{R 21} in the formula (1-2), preferable embodiments thereof are also the same.

[Manufacturing method (Manufacturing method of a specific resin having a repeating unit represented by the formula (1-2))]
When the specific resin has a repeating unit represented by the formula (1-2), the specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.
Further, the method for producing a specific resin having a repeating unit represented by the formula (1-1) includes an imidization step of imidizing the specific resin having the repeating unit represented by the above formula (1-2). But it may be.

In the imidization step, the specific resin having the repeating unit represented by the formula (1-2) obtained in the precursor manufacturing step or the like is imidized, and the repeating unit represented by the formula (1-1) is used. A specific resin to have is obtained.
The imidization step may be any of thermal imidization (for example, imidization by heating), chemical imidization (for example, imidization using a catalyst), and imidization by a combination thereof, for example, an amine compound. It is carried out by heating in the presence of a catalyst such as.
Further, in the imidization step, for example, a dehydrating agent may be used. Examples of the dehydrating agent include carboxylic acid anhydrides such as acetic anhydride.
In addition, the details of imidization can be carried out by a known method.

-Other manufacturing methods-
The method for producing the specific resin having the repeating unit represented by the formula (1-1) is a method of synthesizing the resin in one step by heating and dehydrating at a high temperature during the reaction of the carboxylic acid dianhydride and the diamine compound. There may be.
Examples of the carboxylic acid dianhydride include the carboxylic acid dianhydride represented by the above formula (DC-1). The carboxylic acid dianhydride is preferably a compound obtained in the above-mentioned tetravalent carboxylic acid production step.
As the diamine compound, a diamine compound represented by the above formula (DA-1) can be used.
Further, the method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by decarboxylating at a high temperature during the reaction of the carboxylic acid dianhydride and the diisocyanate compound.
Examples of the carboxylic acid dianhydride include the carboxylic acid dianhydride represented by the above formula (DC-1). The carboxylic acid dianhydride is preferably a compound obtained in the above-mentioned tetravalent carboxylic acid production step.
Examples of the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (DA-1) are changed to isocyanate groups.
For details of these production methods, known methods for synthesizing polyimide can be referred to.

Further, in the method for producing a resin used in the present invention, a compound having three carboxy groups or a derivative of the compound having the above three carboxy groups is reacted with a first diamine compound or a diisocyanate compound. The production method may include a step of obtaining a compound D having two imide ring structures and two carboxylic acids, and a step of reacting the compound D with a second diamine compound to obtain a resin. ..
As the derivative of the above-mentioned compound having three carboxy groups or the above-mentioned compound having three carboxy groups, a compound having three carboxy groups, a compound having one carboxy group and one carboxylic acid anhydride group, and 1 A compound having one carboxylic acid halide group and one carboxylic acid anhydride group, a compound having one carboxylic acid ester group and one carboxylic acid anhydride group, a compound having three carboxylic acid ester groups, and one carboxylic acid. Examples thereof include compounds having an acid halide group and two carboxylic acid ester groups.
Specifically, as the first diamine compound, a diamine compound represented by the above formula (DA-1) can be used.
Specific examples of the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (DA-1) are changed to isocyanate groups.
The conditions and the like of the above reaction may be appropriately determined with reference to known imidization reactions.

Examples of the second diamine compound include diamine compounds represented by the following formula (DA-2).

Wherein (DA-2), ^{L 3} has the same meaning as ^{L 3} in formula (R-1), a preferable embodiment thereof is also the same.
The reaction conditions in the step of obtaining the resin may be appropriately determined with reference to a known method for producing a polyamide.

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

[Photopolymerization initiator]
The curable resin composition of the present invention preferably contains a photopolymerization initiator as the polymerization initiator.
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, IRGACURE 127, and IRGACURE 727 (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-acetoxyiminobutane-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. Further, an oxime compound having the following structure can also be used.

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

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

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 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. Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to 2 interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R ^I01 is a group represented by formula (II), the same as R ^I00 The groups, R ^I02 to R ^I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.

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.

<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.

[Photoacid generator]
Further, the curable resin composition of the present invention may contain a photoacid generator as a polymerization initiator.
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 quinone-diazide compounds include a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide 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.

<Thermal acid generator>
The curable resin composition of the present invention may contain a thermosetting agent as a polymerization initiator.
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 thermosetting agent, 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 during drying (pre-baking: about 70 to 140 ° C.) after applying the curable resin composition to the substrate, 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.

Of these, those that generate alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is 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 methanesulphonate (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methylsulfonium, 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, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane is preferred as the thermoacid generator.

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.

<Polymerizable compound>
The curable resin composition of the present invention preferably contains a polymerizable compound.
In the present specification, the compound corresponding to the above-mentioned specific resin does not correspond to a polymerizable compound.
As the polymerizable compound, a polyfunctional polymerizable compound is preferable. In the present specification, the polyfunctional polymerizable compound means a compound having two or more polymerizable groups.
Further, as the polymerizable compound, a radically polymerizable compound is preferable, and a compound having two or more radically polymerizable groups is more preferable.

[Radical 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.

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. 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 a preferable radically polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. 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. Moreover, the polymerizable property is good. 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. The acid value is measured according to the description of JIS K 0070: 1992.

In the curable resin composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. 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, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate 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, from the viewpoint of pattern resolution and film elasticity, it is also preferable to use bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and 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 diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) addition of bisphenol A Diacrylate, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate having urethane bond, having urethane bond Bifunctional methacrylate can be used. If necessary, two or more of these can be mixed and used. For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.

[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 the number 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® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E (the above products) Name, manufactured by DIC Co., Ltd., 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.) 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.

-Benzoxazine 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, aromatic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, 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 aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like 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- Suitable examples include dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone 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. Further, combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone are also preferable.

From the viewpoint of coatability, the content of the solvent 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 preferable that the amount is 10 to 70% by mass, and 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.

<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 a polyimide different from the specific resin, a polyimide precursor different from the specific resin, polysiloxane, a resin containing a siloxane structure, an epoxy resin, an acrylic resin, and the like.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a cured film having excellent chemical resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the chemical resistance of a cured film, and the like.

[Polyimide (other resin)]
From the viewpoint of the film strength of the obtained cured film, it is preferable that the polyimide, which is another resin, has a repeating unit represented by the above-mentioned formula (4).
In the polyimide, the repeating unit represented by the formula (4) may be one kind, but may be two or more kinds. Further, the polyimide may contain other types of repeating units in addition to the repeating unit of the above formula (4).

As one embodiment of the polyimide in the present invention, a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the repeating unit represented by the formula (4) is exemplified. Will be done. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide 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 polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.

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

[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 other resins may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the 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 types 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 the curable resin composition contains a resin having a repeating unit represented by the formula (1-2) as a specific resin, the curable resin composition preferably contains a thermosetting agent.
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 intramolecular 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 sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermodegradability 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 used as 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, 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 Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, F.C .; 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 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 (Y1-3), 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 diaryl 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 types 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 resin having a repeating unit represented by the formula (1-2) as a specific 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 fused ring in which two monocyclic rings or 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 that 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 may be more preferred.

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 are 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 are 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 preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further 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, an arylalkyl group is preferable for ^{Rb 13.}

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 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 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is 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 types 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, isooxazole 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 , Salicylate 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, 5-phenyltetrazole, 5-methylbenzotriazole and 4-methylbenzotriazole 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-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine , N-nitroso diphenylamine, 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 -Hydroxyquinolin, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitrosophenylhydroxyamine first cerium salt, 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 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.

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 silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, etc. Can be mentioned.

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.

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. .. Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanure, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanabyl Examples thereof include triethoxysilane and 3-trimethoxysilylpropyl succinate anhydride. These can be used alone or in combination of two or more.

Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetate acetate), aluminum tris (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 photobase generator, a chain transfer agent, a surfactant, a higher fatty acid derivative, and an inorganic substance, if necessary. Particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregating agents 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.
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. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is 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.

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171, Novell FC4430, FC4432 (above, manufactured by 3M Japan Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.) ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP2011-132503 can also be used. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.

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

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

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

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

Specifically, as a cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

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 based on 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.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Furthermore, examples of triazine-based ultraviolet absorbers include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-Triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) )-1,3,5-Triazine, 2,4,6-Tris (2-Hydroxy-4-octyloxyphenyl) -1,3,5-Triazine, 2,4,6-Tris [2-Hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-Triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.

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

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

Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Tetraalkoxytitanium compounds: For example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxyside), titanium tetraisobutoxide, titanium tetraisopropoxyside, titanium tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. .. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like. Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).

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

The compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.

Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.

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

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

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 of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

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 is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. 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 pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further 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 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.
Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
These substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

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.
In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method or spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. Depending on the viscosity of the resin composition and the film thickness to be set, it is also preferable to apply the resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. 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.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like. A pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.

<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.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The exposure amount 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 thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm 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, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developing solution is continuously supplied to the base material, a step in which the developing solution is kept in a substantially stationary state on the base material, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a combination thereof. Processes 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 hydrogen carbonate, potassium hydrogen carbonate, 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 TMAH is used, for example, the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.

In solvent development, it is more preferable that the developer contains 90% 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 As tons, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. , Dimethyl sulfoxide is preferably mentioned as the sulfoxides.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable. When the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.
The developer may further contain other components. Examples of other components include known surfactants and known defoamers.

[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.

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 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
In the case of solvent development, rinsing is preferably performed using an organic solvent different from the developing solution.
Examples of the rinsing liquid in the case of solvent development include PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropanol) and the like, and PGMEA is preferable.
In the case of alkaline development, rinsing is preferably performed using pure water.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly specified, but can be preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

Examples of the organic solvent when the rinsing solution contains an organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate) Ethyl acid acid, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran , Ethyl 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene, etc., dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols. Preferred examples of glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

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

When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.

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

[Supplying method of rinse liquid]
The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material. There is a method of continuously supplying the developing solution by means such as a straight nozzle on the top.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sound conditioner or the like and a process of combining them can be adopted.

<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.
Further, when the specific resin is a polyimide precursor and the curable resin composition contains a thermobase generator, in the heating step, for example, a base is generated by decomposition of the thermobase generator, 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. In the case of an oven capable of rapid heating, it is preferable to carry out the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.

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.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing 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.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

<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 species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals are exemplified. Copper and aluminum are more preferred, and copper is even 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.

As the thickness of the metal layer, 0.01 to 100 μm is mentioned as an example in the thickest portion, 0.1 to 50 μm is preferable, and 1 to 10 μm is more preferable.

<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 drying step, the 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. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

For example, a configuration in which the number of resin layers is 2 or more and 20 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is given as an example, and the number of resin layers is 3 or more and 7 or less. Is preferable, and 3 layers or more and 5 layers or less are more preferable.

<Surface activation treatment process>
The method for producing a cured film of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then the metal layer forming step. Good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF ₄ / O ₂ , NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / ^{m 2,} more preferably 1000 ~ 100,000J / ^{m 2,} and most preferably 10,000 ~ 50,000J / ^{m 2.}

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 the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are 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 taken into consideration. Yes, these contents are incorporated herein.

(resin)
The resin of the present invention may contain at least one selected from the group consisting of the repeating unit represented by the above formula (2-1) and the repeating unit represented by the above formula (2-2). preferable.
The resin of the present invention contains at least one selected from the group consisting of the repeating unit represented by the above formula (2-1) and the repeating unit represented by the above formula (2-2). Is synonymous with 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.

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 into. 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-9) 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-9) having the following structures were synthesized by using dinitro compounds (A-2) to (A-9) instead of the dinitro compound (A-1). ..

<Synthesis of carboxylic acid dianhydride>
In a flask equipped with a condenser and a stirrer, 18.5 g (0.88 mol) of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 g of ethyl acetate and cooled to −10 ° C. or lower. Then, 10.6 g (40 mmol) of diamine (AA-1) and 7.12 g (90 mmol) of pyridine were dissolved in 60 g of ethyl acetate, and this was added dropwise over 1 hour. After the dropping, the mixture was stirred at −10 ° C. or lower for 1 hour and at 25 ° C. for 1 hour. Then, 500 mL of ethyl acetate and 300 mL of water were added, and after stirring for 10 minutes, this was transferred to a separating funnel, washed with 300 mL of water, washed twice with 200 mL of saturated aqueous sodium hydrogen carbonate, and 200 mL of dilute aqueous hydrochloric acid solution. The cells were washed in the order of aqueous solution and saturated brine. This was dried over magnesium sulfate, concentrated on an evaporator, and then the ethyl acetate solution was crystallized into hexane. This was filtered and vacuum dried to obtain 20.0 g of anhydride (MA-1). It was confirmed from the NMR spectrum that it was an anhydride (MA-1). ^{The results of 1} H-NMR analysis of the anhydride (MA-1) are shown below.
^{1 1} H-NMR data (heavy dimethyl sulfoxide (DMSO), 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.88 (s, 3H), 4.44-4.47 (q, 2H), 4.60-4.62 (q, 2H), 5.70 (s, 2H), 6 .06 (s, 1H), 8.23-8.26 (m, 4H), 8.52-8.54 (d, 2H), 8.65 (s, 2H), 8.82-8.83 (T, 1H), 10.98 (s, 2H)
Similarly, in the synthesis of the anhydride (MA-1), by using diamines (AA-2) to (AA-7) instead of the diamine (AA-1), the anhydride (MA-2) having the following structure is used. )-(MA-7) was synthesized.
In the synthesis of the anhydride (MA-1), the anhydride (MA-8) was synthesized by using 4,4'-diaminobenzanilide instead of the diamine (AA-1).
In the synthesis of the anhydride (MA-1), the anhydride (MA-9) was synthesized by using a diamine (AA-10) having the following structure instead of the diamine (AA-1).
Diamine (AA-10) is prepared by reacting diamine (AA-1) with 4-nitrobenzoyl chloride to prepare a dinitro compound (A-10), and then the dinitro compound (A-10) is converted into a dinitro compound. The diamine (AA-1) was reduced from (A-1) by the same method as in the case of synthesizing the diamine (AA-1).
By using diamine (AA-8) or (AA-9) instead of diamine (AA-1) in the synthesis of anhydride (MA-1), (MA-10) and (MA-11) having the following structures are used. ) Was synthesized respectively.

<Synthesis of polyimide resin PI-1>
11.0 g (18 mmol) of anhydride (MA-1), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 4.76 g (18 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-1. The molecular weight of PI-1 was Mw (weight average molecular weight) = 62,100 and Mn (number average molecular weight) = 22,900.
The structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).

<Synthesis of polyimide resin PI-2>
9.73 g (18 mmol) of anhydride (MA-2), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 5.01 g (18 mmol) of diamine (AA-4) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 34.4 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-2. The molecular weight of PI-2 was Mw = 74,200 and Mn = 29,000.
The structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).

<Synthesis of polyimide resin PI-3>
9.45 g (18 mmol) of anhydride (MA-3), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 8.27 g (18 mmol) of diamine (AA-6) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-3. The molecular weight of PI-3 was Mw = 81,000 and Mn = 32,700.
The structure of PI-3 is presumed to be the structure represented by the following formula (PI-3).

<Synthesis of polyimide resin PI-4>
In a flask equipped with a condenser and a stirrer, while removing water, 11.0 g (18 mmol) of anhydride (MA-1), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 5.01 g (18 mmol) of diamine (AA-4) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-4. The molecular weight of PI-4 was Mw = 81,000 and Mn = 32,700.
The structure of PI-4 is presumed to be the structure represented by the following formula (PI-4).

<Synthesis of polyimide resin PI-5>
11.0 g (18 mmol) of anhydride (MA-1), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 3.75 g (18 mmol) of diamine (AA-7) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-5. The molecular weight of PI-5 was Mw = 32,600 and Mn = 14,100.
The structure of PI-5 is presumed to be the structure represented by the following formula (PI-5).

<Synthesis of polyimide resin PI-6>
15.31 g (18 mmol) of anhydride (MA-9), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 7.81 g (17 mmol) of diamine (AA-6) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-6. The molecular weight of PI-6 was Mw = 28,400 and Mn = 11,300.
The structure of PI-6 is presumed to be the structure represented by the following formula (PI-6).

<Synthesis of polyimide resin PI-7>
11.5 g (18 mmol) of anhydride (MA-10), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. 0.02 g of (manufactured by Kogyo Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 4.76 g (18 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (NMP). 50 g was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide resin PI-7. The molecular weight of PI-7 was Mw (weight average molecular weight) = 35,500 and Mn (number average molecular weight) = 13,900.
The structure of PI-7 is presumed to be the structure represented by the following formula (PI-7).

<Synthesis example of polyimide precursor resin PA-1>
In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 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 and 11.9 g (45 mmol) of diamine (AA-1) was added to 80 mL of N-methylpyrrolidone (NMP). The dissolved product 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 PA-1. The molecular weight of this polyimide precursor PA-1 was Mw = 30,600 and Mn = 13,500.
The structure of PA-1 is presumed to be the structure represented by the following formula (PA-1).

<Synthesis example of polyimide precursor resin PA-2>
In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 g of diglyme while removing water. 8.56 g (75 mmol) of trifluoro-1-propanol, 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 and 11.9 g (45 mmol) of diamine (AA-1) was added to 80 mL of N-methylpyrrolidone (NMP). The dissolved product 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 PA-2. The molecular weight of this polyimide precursor PA-2 was Mw = 28,300 and Mn = 12,900.
The structure of PA-2 is presumed to be the structure represented by the following formula (PA-2).
In formula (PA-2), * represents the binding site with the oxygen atom to which ^{R 1 binds.}

<Synthesis example of polyimide precursor resin PA-3>
12.5 g (45 mmol) of diamine (AA-4), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (Tokyo Chemical Industry) while removing water in a flask equipped with a condenser and a stirrer. (Manufactured by Co., Ltd.) 0.05 g was dissolved in 122 g of N-methylpyrrolidone (NMP). Then 28.2 g (45 mmol) of anhydride (MA-4) was added and stirred at 25 ° C. for 5 hours. Then, after adding 40 g of N-methylpyrrolidone (NMP), the polyimide precursor resin was 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 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a polyimide precursor PA-3. The molecular weight of this polyimide precursor PA-3 was Mw = 50,300 and Mn = 21,500.
The structure of PA-3 is presumed to be the structure represented by the following formula (PA-3).

<Synthesis example of polyimide precursor resin PA-4>
In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 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 and 9.37 g (45 mmol) of diamine (AA-7) was added to 80 mL of N-methylpyrrolidone (NMP). The dissolved product 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 PA-4. The molecular weight of this polyimide precursor PA-4 was Mw = 21,900 and Mn = 10,100.
The structure of PA-4 is presumed to be the structure represented by the following formula (PA-4).

<Synthesis example of polyimide precursor resin PA-5>
In a flask equipped with a condenser and a stirrer, 40.7 g (47.8 mmol) of anhydride (MA-9) was suspended in 180 g of diglyme while removing water. 16.4 g (100 mmol) of triethylene glycol monomethyl 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 50 mL of N-methylpyrrolidone (NMP) was added and 11.89 g (45 mmol) of diamine (AA-1) was added to 100 mL of N-methylpyrrolidone (NMP). The dissolved product 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 PA-5. The molecular weight of this polyimide precursor PA-5 was Mw = 28,000 and Mn = 13,500.
The structure of PA-5 is presumed to be the structure represented by the following formula (PA-5).

<Synthesis example of polyimide precursor resin PA-6>
In a flask equipped with a condenser and a stirrer, 29.5 g (47.8 mmol) of anhydride (MA-11) was suspended in 100 g of diglyme while removing water. 4.61 g (100 mmol) of ethanol 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 11.9 g (45 mmol) of diamine (AA-1) was added to 80 mL of N-methylpyrrolidone (NMP). The dissolved product 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 PA-6. The molecular weight of this polyimide precursor PA-6 was Mw = 25,100 and Mn = 10,500.
The structure of PA-6 is presumed to be the structure represented by the following formula (PA-6).

<Synthesis of Polyimide P-1 for Comparative Example>
In a flask equipped with a condenser and a stirrer, while removing water, 11.4 g (25 mmol) of anhydride (a-1) represented by the following formula (a-1) was added to N-methylpyrrolidone (NMP) 33. Dissolved in 1 g. Next, 2.70 g (25 mmol) of 1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (N-methylpyrrolidone (NMP). NMP) 50 g was added and diluted.
The reaction was precipitated in 1.2 liters of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain Polyimide P-1 for Comparative Example. The molecular weight of P-1 was Mw = 74,300 and Mn = 30,100.
The structure of P-1 is presumed to be the structure represented by the following formula (P-1).
Since P-1 does not have a polymerizable group at the position corresponding to ^{L 11} in the formula (1-1), it does not correspond to the specific resin.

<Synthesis of polyimide precursor P-2 for comparative example>
In a flask equipped with a condenser and a stirrer, 21.8 g (47.8 mmol) of anhydride (a-1) was suspended in 100 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. Next, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 1.3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.87 (45 mmol) was added to 50 mL of NMP. The solution dissolved therein 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 Polyimide P-2 for Comparative Example. The molecular weight of this polyimide precursor P-2 was Mw = 26,300 and Mn = 12,100.
The structure of P-2 is presumed to be the structure represented by the following formula (P-2).
Since P-2 does not have a polymerizable group at the position corresponding to ^{L 21} in the formula (1-2), it does not correspond to the specific resin.

<Synthesis of polyimide precursor P-3 for comparative example>
In a flask equipped with a condenser and a stirrer, while removing water, 2.31 g (12.5 mmol) of 1,12-dodecanediamine, 1.41 g (5.7 mmol) of 4,4'-diaminodiphenyl sulfone and N- 5.0 g of methylpyrrolidone was added and the mixture was stirred at room temperature for 15 minutes. Next, a mixed solution of 10.00 g (19.1 mmol) of 1,10- (decamethylene) bistrimeritate dianhydride and 10.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the temperature of the obtained mixed solution was raised to 60 ° C. and stirred for 8 hours to obtain an NMP solution of the polyimide precursor P-3 for Comparative Example. The solid content in the obtained solution was 40% by mass, the Mw of P-3 was 42,000, and Mn = 20,000.
Since P-3 does not have a polymerizable group at the position corresponding to ^{L 21} in the formula (1-2), it does not correspond to the specific resin.

<Examples and Comparative Examples>
In each example, the components shown in Table 1 below were mixed to obtain each curable resin composition. Further, in each Comparative Example, the components shown in Table 1 below were mixed to obtain each comparative composition. The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
In Table 1, the numerical value in the column of "parts by mass" indicates the content (parts by mass) of each component.
In Table 1, for example, the description of "PA-1 / PI-1" in the "Type" column and "18/14" in the "Mass part" column indicates that PA-1 is 18 parts by mass and PI-1. Is shown to have been used in each of 14 parts by mass.
Further, in Table 1, the description of "-" indicates that the corresponding component is not contained.

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

[Resin (specific resin or comparative resin)]
-PI-1 to PI-7: Polyimide resins PI-1 to PI-7 synthesized above
-PA-1 to PA-6: Polyimide precursor resins PA-1 to PA-6 synthesized above.
-P-1 to P-3: Comparative polyimide P-1 synthesized above, comparative polyimide precursors P-2 to P-3.

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

[Photopolymerization initiator]
・ 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)
-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 (manufactured by Tokyo Chemical Industry Co., Ltd.) )

[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 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 1 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. The dissolution rate (nm / min) was calculated by comparing the film thicknesses before and after.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Chemical resistance" column of Table 1. 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.

[Evaluation of developer solubility (developability)]
The developer solubility evaluation was carried out as follows.
Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a silicon wafer by 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 obtain a uniform curable resin composition layer having a thickness of 35 μm on the silicon wafer.
The curable resin composition layer on the silicon wafer was exposed to i-rays with an exposure energy of ^{500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).} The above exposure was performed using a binary mask in which a 1: 1 line-and-space pattern having a width of 50 μm, a width of 70 μm, or a width of 100 μm was formed.
With respect to the curable resin composition layer after exposure, in the example described as "solvent" in the column of "development method (developer)" in Table 1, with respect to the curable resin composition layer after exposure. Development was carried out using cyclopentanone at 30 ° C. as a developing solution, and rinsing was carried out with PGMEA (propylene glycol monomethyl ether acetate).
In the example described as "alkali" in the column of "development method (developer)" in Table 1, 2.38 mass% tetra at 30 ° C. as a developer with respect to the curable resin composition layer after exposure. Development was carried out using an aqueous solution of methylammonium hydroxide, and rinsing was carried out with ion-exchanged water.
The minimum development time is the minimum time required to dissolve the unexposed area when the thickness of the curable resin composition layer is 35 μm using a 1: 1 line-and-space (L / S) pattern with a width of 100 μm during exposure. And evaluated according to the following evaluation criteria. It can be said that the shorter the minimum development time, the better the developer solubility. The evaluation results are shown in the "Developability" column of Table 1.
-Evaluation criteria-
A: The minimum development time was within 30 seconds.
B: The minimum development time was more than 30 seconds and less than 60 seconds.
C: The minimum development time was more than 60 seconds and less than 120 seconds.
D: Not completely dissolved in 120 seconds.

[Resolution evaluation]
In each Example or Comparative Example, a copper-clad laminate having a curable resin composition layer was produced by the same method as in the developer solubility evaluation, and a 1: 1 line-and-space pattern having a width of 70 μm or a width of 100 μm was produced. Exposure using (L / S pattern) was performed.
The development time is the same as that of the developer solubility evaluation, except that the development time is twice the minimum development time in the developer solubility evaluation, and then the development treatment and the rinsing treatment are performed and then dissolved. We observed the part where the copper surface appeared and confirmed whether the resolution could be achieved.
Twenty-seven points were measured for the dissolved part in the pattern of the cured film after development, and the evaluation was made according to the following evaluation criteria. The evaluation results are listed in the "Resolution" column of Table 1.
-Evaluation criteria-
A: All 50 μm L / S patterns could be resolved.
B: At 50 μm, one or more were not resolved, and all 70 μm L / S patterns could be resolved.
C: One or more of the 70 μm L / S patterns were not completely resolved, and all 100 μm L / S patterns could be resolved.
D: One or more of the 100 μm L / S patterns were not completely resolved due to development residue and the like.

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 3 do not contain a specific resin. It can be seen that the comparative compositions according to Comparative Examples 1 to 3 are inferior in chemical resistance.

<Example 101>
The curable resin composition 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 column of "curing conditions" of Example 1 in Table 1, heating was performed at this temperature for 3 hours. An interlayer insulating film for the rewiring layer was formed. The interlayer insulating film for the rewiring layer was excellent in insulating property. 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

A resin having at least one repeating unit selected from the group consisting of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (1-2), and
Including polymerization initiator,
Curable resin composition;

In formula (1-1), R 11 represents a tetravalent group having a plurality of amide bonds, and L 11 represents a divalent linking group containing a polymerizable group;
In formula (1-2), R 21 is a tetravalent group having a plurality of amide bonds, L 21 represents a divalent group containing a polymerizable group, and R 22 and R 23 are independent hydrogen atoms. Or represents a monovalent organic group.
The resin has a repeating unit represented by the following formula (2-1) as a repeating unit represented by the formula (1-1), or a repeating unit represented by the formula (1-2). The curable resin composition according to claim 1, which has a repeating unit represented by the following formula (2-2).

In formula (2-1), X 1 and X 2 are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms, cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. A group is represented, Y 1 represents an organic group having 1 to 30 carbon atoms, Q 1 represents an organic group having 1 to 30 carbon atoms, and A 1 represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy. Represents a group containing at least one group selected from the group consisting of groups, A 2 represents a group containing a polymerizable group, and R 1 and R 2 each independently contain a hydrogen atom or a monovalent organic group. Represented, n1 and n2 each independently represent an integer of 1 or more;
In formula (2-2), X 3 and X 4 are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y 2 represents an organic group having 1 to 30 carbon atoms, Q 2 represents an organic group having 1 to 30 carbon atoms, and A 3 represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A 4 represents a group containing a polymerizable group, and R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group. , G 1 and G 2 each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer of 1 or more.
X 1 and X 2 in the formula (2-1) are independent aromatic hydrocarbon groups having 6 to 30 carbon atoms, and X 3 and X 4 in the formula (2-2) are independent, respectively. The curable resin composition according to claim 2, which is an aromatic hydrocarbon group having 6 to 30 carbon atoms.
Claim 2 or claim 2, wherein Y 1 in the formula (2-1) is a group containing an aromatic hydrocarbon group, and Y 2 in the formula (2-2) is a group containing an aromatic hydrocarbon group. The curable resin composition according to 3.
Claims 2 to 2, wherein Q 1 in the formula (2-1) is a group containing an aromatic hydrocarbon group, and Q 2 in the formula (2-2) is a group containing an aromatic hydrocarbon group. The curable resin composition according to any one of 4.
The curable resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound.
The curable resin composition according to claim 6, further comprising a polyfunctional polymerizable compound as the polymerizable compound.
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 laminated body 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.
Includes at least one selected from the group consisting of the repeating unit represented by the formula (2-1) and the repeating unit represented by the formula (2-2).
resin.

In formula (2-1), X 1 and X 2 are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y 1 represents an organic group having 1 to 30 carbon atoms, Q 1 represents an organic group having 1 to 30 carbon atoms, and A 1 represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A 2 represents a group containing a polymerizable group, and R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group. , N1 and n2 each independently represent an integer greater than or equal to 1.
In formula (2-2), X 3 and X 4 are independently aromatic hydrocarbon groups having 6 to 30 carbon atoms and cyclic, linear or branched aliphatic groups having 2 to 30 carbon atoms. Y 2 represents an organic group having 1 to 30 carbon atoms, Q 2 represents an organic group having 1 to 30 carbon atoms, and A 3 represents a polymerizable group, an aliphatic hydrocarbon group, and a polyalkyleneoxy group. Represents a group containing at least one group selected from the group consisting of, A 4 represents a group containing a polymerizable group, and R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group. , G 1 and G 2 each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer of 1 or more.