TW202112907A - Curable resin composition, cured film, layered product, method for producing cured film, semiconductor device, resin, and method for producing resin - Google Patents

Abstract

A curable resin composition comprising a resin having repeating units represented by formula (1-1) and a solvent; a cured film obtained by curing the curable resin composition; a layered product including the cured film; a method for producing the cured film; a semiconductor device including the cured film or the layered product; and a resin having repeating units represented by formula (1-1) and a method for producing the resin. In formula (1-1), X1 and X2 each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y1 represents an (n+2)-valent organic group, A1 represents a group including a polymerizable group, n is an integer of 1 or larger, and Q1 represents a divalent linking group.

Description

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

The present invention relates to a curable resin composition, a cured film, a laminate, a method of manufacturing a cured film, a semiconductor device, a resin, and a method of manufacturing a resin.

Polyimide is suitable for various applications due to its excellent heat resistance and insulation properties. The use is not particularly limited, and if a semiconductor device for packaging is taken as an example, the use as a material of an insulating film or a sealing material or a protective film can be cited. It is also used as a base film or cover film (COVERLAY) for flexible substrates.

For example, in the above-mentioned applications, polyimine is sometimes used in the form of a curable resin composition containing polyimine. These curable resin compositions can be applied to substrates and the like by known coating methods, etc., so it can be said that they are excellent in manufacturing adaptability, such as the shape, size, and application position of the applied curable resin composition The degree of freedom of design is high. From the viewpoint that polyimide not only has high performance, but also has excellent manufacturing adaptability, it is increasingly expected to expand the industrial application of curable resin compositions containing polyimide.

For example, Patent Document 1 describes a polyimide precursor, which is a polyimide precursor obtained by reacting a tetracarboxylic dianhydride component and a diamine component, wherein the tetracarboxylic dianhydride component Department of a compound of a specific structure. In addition, Patent Document 2 describes a photosensitive resin composition comprising: (A) a polyamide acid having a specific structural unit; (B) a photopolymerizable compound; and (C) a photopolymerization initiator .

[Patent Document 1] JP 2014-172994 A [Patent Document 2] JP 2009-251451 A

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

The object of one embodiment of the present invention is to provide a curable resin composition having excellent chemical resistance of the cured film obtained, a cured film formed by curing the curable resin composition, and a laminate containing the cured film A body, a method of manufacturing the cured film, and a semiconductor device including the cured film or the laminated body. In addition, the purpose of another embodiment of the present invention is to provide a novel resin and a method for manufacturing the above-mentioned resin.

式（1-1）中，X¹ 及X² 分別獨立地表示芳香族烴基或脂肪族環基，Y¹ 表示n+2價有機基，A¹ 表示包含聚合性基之基團，n表示1以上的整數，Q¹ 表示2價連接基。 ＜2＞如＜1＞所述之硬化性樹脂組成物，其中，上述A¹ 係作為聚合性基包含包括乙烯性不飽和鍵之基團、環狀醚基或羥甲基之基團。 ＜3＞如＜1＞或＜2＞所述之硬化性樹脂組成物，其中，還包含聚合起始劑及聚合性化合物。 ＜4＞如＜1＞或＜2＞所述之硬化性樹脂組成物，其中，還包含酸產生劑及酸交聯劑。 ＜5＞如＜1＞至＜4＞之任一項所述之硬化性樹脂組成物，其中，上述Q¹ 包含選自包括由下述式（A-1）～式（A-5）表示之結構之群組中之至少一種結構。 [化學式2]

在式（A-1）～（A-5）中，R^A11 ～R^A14 、R^A21 ～R^A24 、R^A31 ～R^A38 、R^A41 ～R^A48 及R^A51 ～R^A58 分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基、鹵素原子或包含聚合性基的基團，L^A31 及L^A41 分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，*分別獨立地表示與其他結構的鍵結部位。 ＜6＞如＜1＞至＜5＞之任一項所述之硬化性樹脂組成物，其中，上述Q¹ 包含含有聚合性基之基團。 ＜7＞如＜1＞至＜6＞之任一項所述之硬化性樹脂組成物，其中，Y¹ 係n+2價烴基。 ＜8＞如＜1＞至＜7＞之任一項所述之硬化性樹脂組成物，其中，其係用於形成再配線層用層間絕緣膜。 ＜9＞一種硬化膜，其係藉由使＜1＞至＜8＞之任一項所述之硬化性樹脂組成物硬化而成。 ＜10＞一種積層體，其係具有兩層以上的＜9＞所述之硬化膜，在任意上述硬化膜彼此之間具有金屬層。 ＜11＞一種硬化膜的製造方法，其係包括將＜1＞至＜8＞之任一項所述之硬化性樹脂組成物適用於基板而形成膜之膜形成製程。 ＜12＞如＜11＞所述之硬化膜的製造方法，其係包括在50～450℃下加熱上述膜之製程。 ＜13＞一種半導體器件，其係具有＜9＞所述之硬化膜或＜10＞所述之積層體。 ＜14＞一種樹脂，其係具有由下述式（1-1）表示之重複單元。 [化學式3]

式（1-1）中，X¹ 及X² 分別獨立地表示芳香族烴基或脂肪族環基，Y¹ 表示n+2價有機基，A¹ 表示包含聚合性基之基團，n表示1以上的整數，Q¹ 表示2價連接基。 ＜15＞一種樹脂的製造方法，其係製造＜14＞所述之樹脂之製造方法，其係包括： 使具有至少兩個羥基和至少一個反應性基之化合物A和具有可以與上述反應性基形成鍵之基團及聚合性基之化合物B反應，從而得到二醇化合物之製程； 使上述二醇化合物和具有3個羧基之化合物或上述具有3個羧基之化合物的衍生物反應，從而得到具有兩個酯鍵之4價羧酸化合物之製程； 使上述4價羧酸化合物和二胺化合物反應而得到聚醯亞胺前驅物之製程；及 使上述聚醯亞胺前驅物醯亞胺化之製程。 [發明效果]Hereinafter, examples of representative embodiments of the present invention are described. <1> A curable resin composition containing a resin and a solvent having a repeating unit represented by the following formula (1-1). [Chemical formula 1]

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group. <2> The curable resin composition according to <1>, wherein the A ¹ system includes, as a polymerizable group, a group including an ethylenically unsaturated bond, a cyclic ether group, or a methylol group. <3> The curable resin composition as described in <1> or <2>, which further contains a polymerization initiator and a polymerizable compound. <4> The curable resin composition as described in <1> or <2>, which further contains an acid generator and an acid crosslinking agent. <5> The curable resin composition according to any one of <1> to <4>, wherein the Q ^{1 is} selected from among those represented by the following formulas (A-1) to (A-5) At least one structure in the group of structures. [Chemical formula 2]

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 each independently represent a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxyl group, cyano group, halogenated alkyl group, halogen atom or group containing a polymerizable group, L ^A31 and L ^A41 each independently represent a single bond, a carbonyl group, a sulfonyl group , A divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group or a halogenated alkylene group, * each independently represents a bonding site with another structure. <6> The curable resin composition according to any one of <1> to <5>, wherein the Q ¹ includes a polymerizable group-containing group. <7> The curable resin composition according to any one of <1> to <6>, wherein Y ¹ is an n+divalent hydrocarbon group. <8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer. <9> A cured film formed by curing the curable resin composition described in any one of <1> to <8>. <10> A layered product having two or more layers of the cured film described in <9>, and having a metal layer between any of the cured films. <11> A method for producing a cured film, which includes a film forming process of applying the curable resin composition described in any one of <1> to <8> to a substrate to form a film. <12> The method for producing a cured film as described in <11>, which includes a process of heating the film at 50 to 450°C. <13> A semiconductor device having the cured film described in <9> or the laminated body described in <10>. <14> A resin having a repeating unit represented by the following formula (1-1). [Chemical formula 3]

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group. <15> A method for producing a resin, which is the method for producing the resin described in <14>, which includes: making a compound A having at least two hydroxyl groups and at least one reactive group and having a compound A that can interact with the above-mentioned reactive group The process of reacting the bond-forming group and the polymerizable compound B to obtain a diol compound; reacting the above diol compound with a compound having 3 carboxyl groups or a derivative of the above compound having 3 carboxyl groups to obtain The process of producing a tetravalent carboxylic acid compound with two ester bonds; the process of reacting the aforementioned tetravalent carboxylic acid compound with a diamine compound to obtain a polyimine precursor; and the process of making the aforementioned polyimine precursor imidized Process. [Effects of the invention]

According to one embodiment of the present invention, there is provided a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, The manufacturing method of the said cured film, and the semiconductor device containing the said cured film or the said laminated body. In addition, according to another embodiment of the present invention, a novel resin and a method for manufacturing the above-mentioned resin are provided.

Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiment. In this specification, the numerical range indicated by the symbol "～" refers to the range that includes the numerical values described before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only refers to an independent process, as long as it can achieve the expected effect of the process, it also refers to a process that cannot be clearly distinguished from other processes. In the expression of groups (atomic groups) in this specification, expressions that do not indicate substitution and unsubstituted also include groups without substituents (atomic groups) and groups with substituents (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used for exposure, actinic rays or radiation such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" refers to both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid". "Both or either of them, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of the total mass of the composition excluding other components of the solvent. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and protecting columns HZ-L and TSKgel Super HZM-M as the columns. , TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. In addition, unless otherwise specified, the detection in GPC measurement uses a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is only necessary that another layer exists above or below the layer that becomes the reference among the plurality of layers of interest. That is, the third layer or the third element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference does not need to contact the other layers. Also, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "up", or when a curable resin composition layer is present, the direction from the substrate to the curable resin composition layer is referred to as "Up", the opposite direction is called "down". In addition, this setting of the up and down direction is for the convenience of description of this specification. In the actual situation, the "up" direction in this specification may be different from the vertical upward direction. In this specification, unless otherwise specified, as each component included in the composition, the composition may also include two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C and the air pressure is 101,325 Pa (1 atmosphere). In this specification, a combination of a better aspect is a better aspect.

式（1-1）中，X¹ 及X² 分別獨立地表示芳香族烴基或脂肪族環基，Y¹ 表示n+2價有機基，A¹ 表示包含聚合性基之基團，n表示1以上的整數，Q¹ 表示2價連接基。(Curable resin composition) The curable resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") includes a resin having a repeating unit represented by the following formula (1-1) and a solvent. [Chemical formula 4]

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group.

The curable resin composition of the present invention preferably further contains a polymerization initiator and a polymerizable compound, and more preferably further contains a photoradical polymerization initiator and a radical polymerizable compound. In addition, the curable resin composition of the present invention preferably further includes an acid generator and an acid crosslinking agent, and more preferably further includes a photoacid generator and an acid crosslinking agent. The curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition. The negative-type curable resin composition refers to a composition in which the unexposed part (non-exposed part) is removed by the developer when the layer formed of the curable resin composition is exposed. In addition, a layer formed of such a curable resin composition is called a negative-type curable resin composition layer. The positive curable resin composition refers to a composition in which the exposed part (exposure part) is removed by the developer when the layer formed of the curable resin composition is exposed. In addition, a layer formed of such a curable resin composition is called a positive-type curable resin composition layer. The curable resin composition can be, for example, a negative type curable resin composition by further containing a polymerization initiator and a polymerizable compound. In addition, the curable resin composition can be, for example, a negative curable resin composition by further including a photoacid generator and an acid crosslinking agent. In addition, the curable resin composition further includes a photoacid generator, a radical polymerization initiator (preferably a thermal radical polymerization initiator) and a radical polymerizable compound, or further includes a photoacid generator and an acid. The crosslinking agent can be, for example, a positive curable resin composition. In these aspects, for example, alkaline development is performed after exposure, and the pattern is hardened by heating or the like after development, thereby forming a positive pattern in which the exposed portion is removed.

The cured film obtained by the curable resin composition of the present invention is excellent in chemical resistance. The mechanism by which the above-mentioned effect is obtained is uncertain, but it is presumed to be 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 previously used polyimide resin, the specific resin has an ester bond in the repeating unit represented by the formula (1-1), and has a polymerizable group between the aforementioned ester bonds. It is presumed that by setting it as such, the amount of highly reactive polymerizable groups contained in the resin is increased, and therefore the crosslink density in the cured film (crosslinks formed by the crosslinking of the polymerizable groups) The density of the structure) increases, and a cured film with excellent chemical resistance can be obtained. Since the cured film is excellent in chemical resistance, for example, when the cured film formed by curing the curable resin composition of the present invention, another curable resin composition containing a solvent is further applied and cured to produce a laminate, etc. , Even if the cured film comes into contact with the developer or other curable resin composition, the dissolution of the cured film is suppressed. According to the present invention, a hardened film can be obtained, such as polar solvents such as para-dimethyl sulfide (DMSO) and N-methylpyrrolidone (NMP), and alkalis such as tetramethylammonium hydroxide (TMAH) aqueous solution. The solubility of the aqueous solution or the mixed solution of the polar solvent and the alkaline aqueous solution is suppressed, and the chemical resistance is excellent. In addition, by introducing the above-mentioned ester bond into the resin, the transparency of the resin is improved. Therefore, when a curable resin composition layer is formed using a composition containing the above-mentioned resin, and a patterned cured film is formed by pattern exposure and development, the resolution of the pattern is easily improved. In addition, when the curable resin composition layer is a negative curable resin composition layer, the transparency of the resin is improved, and therefore exposure light is easily transmitted. Therefore, in the crosslinking by exposure, the crosslinking density in the cured film increases, and it is easier to obtain a cured film with excellent chemical resistance. Furthermore, when the curable resin composition layer is a negative curable resin composition layer, the transparency of the resin is improved, whereby exposure light can easily reach the deep portion of the curable resin composition layer. Therefore, the crosslinking density is also increased especially in the deep part of the cured film, and it is easy to obtain a cured film having excellent chemical resistance in the deep part of the cured film. Here, the deep part of the curable resin composition layer refers to the part of the curable resin composition layer on the side opposite to the exposed side. When the curable resin composition layer is formed on the substrate, the When exposure is performed on the opposite side of the curable resin composition layer, the base-side part of the curable resin composition layer is referred to as the deep part of the curable resin composition layer. That is, according to the curable resin composition of the present invention, for example, when exposed from the side opposite to the base material, it is easy to obtain a cured film with excellent chemical resistance in the base-side portion of the curable resin composition layer .

Here, in Patent Documents 1 and 2, there is no description or suggestion regarding the resin having the repeating unit represented by the formula (1-1). In addition, the curable resin composition of Patent Document 1 or 2 has a problem that the cured film obtained has low chemical resistance.

＜Specific resins＞ The curable resin composition of the present invention contains a specific resin. The specific resin has a repeating unit represented by formula (1-1). The specific resin may have a repeating unit represented by formula (1-1) on the side chain, but it is preferable to have a repeating unit represented by formula (1-1) on the main chain. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

[Repeating unit represented by the formula (1-1)] -X ¹ , X ² -In the formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, from the viewpoint of chemical resistance From the viewpoints of solubility and solvent solubility, an aromatic hydrocarbon group is preferred. As the above-mentioned 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 10 carbon atoms is more preferable. The structure with 3 hydrogen atoms removed is better. As the above-mentioned aliphatic ring group, an aliphatic ring group having 6 to 30 carbon atoms is preferred, an aliphatic ring group having 6 to 20 carbon atoms is more preferred, and an aliphatic ring group having 6 to 10 carbon atoms is more preferred. It is better to remove 3 hydrogen atoms from the aliphatic ring structure of the 6-membered ring structure. The aliphatic cyclic group may be a saturated aliphatic cyclic group or an unsaturated aliphatic cyclic group, but a saturated aliphatic cyclic group is preferred. The aliphatic ring group may be an aliphatic hydrocarbon ring group or an aliphatic heterocyclic group, but an aliphatic hydrocarbon ring group is preferred. Among them, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred.

In ^{the aromatic hydrocarbon group or aliphatic ring group of X 1} or X ² , the two positions bonded to the imine structure in formula (1-1) are adjacent to each other in the aromatic hydrocarbon group or aliphatic ring group The location is better. In this specification, the adjacent positions where two bonding sites exist in the ring structure refer to a ring member in the above-mentioned ring structure where a certain bonding site exists and a ring in the above-mentioned ring structure where another bonding site exists Members are adjacent ring members in the ring structure. For example, when the ring structure is a benzene ring structure, adjacent positions are ortho positions.

在式（1-2-1）～式（1-2-6）中，Y¹ 、A¹ 、n、Q¹ 分別與式（1-1）中的Y¹ 、A¹ 、n、Q¹ 的含義相同，且較佳態樣亦相同。In addition, from the viewpoint of developability and solvent solubility, the repeating unit represented by formula (1-1) is represented by any of the following formulas (1-2-1) to (1-2-6) The repeating unit is preferred, the repeating unit represented by formula (1-2-1) or formula (1-2-2) is more preferred, and the repeating unit represented by formula (1-2-1) is even more preferred . [Chemical formula 5]

In the formula (1-2-1) to (1-2-6), in ^{Y 1, A 1, n,} Q 1 , respectively formula ^{(1-1) Y 1, A 1} , n, Q 1 The meanings are the same, and the preferred aspects are also the same.

-A ¹ -In the formula (1-1), A ¹ represents a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferred, and a vinyl group, (meth)allyl group, (meth)acrylamido group, (methyl) group ) Allyloxy group, maleimide group, vinyl phenyl group, epoxy group, oxetanyl group or hydroxymethyl group are more preferred, (meth)acryloyloxy group, (methyl) An acrylamide group, an epoxy group, or a methylol group is more preferable. The number of polymerizable groups contained in A ¹ is one or more, preferably 1-15, more preferably 1-10, more preferably 1-5, particularly preferably one or two, and one is optimal.

式（P-1）中，L¹ 表示單鍵或m+1價連接基，A² 表示聚合性基，m表示1以上的整數，*表示與Y¹ 的鍵結部位。 式（P-1）中，L¹ 係單鍵或烴基、醚鍵、羰基、硫醚鍵、磺醯基、-NR^N -、或者將該等鍵結兩個以上之基團為較佳，單鍵或烴基、醚鍵，羰基，-NR^N -或者將該等鍵結兩個以上之基團為更佳。 上述R^N 表示氫原子或烴基，氫原子、烷基或芳基為更佳，氫原子或烷基為進一步較佳，氫原子為特佳。 作為上述L¹ 中之烴基，碳數1～30的飽和脂肪族烴基、碳數6～30的芳香族烴基或者由該等的組合表示之基團為較佳，碳數1～10的飽和脂肪族烴基、從苯環中去除兩個以上氫原子之基團、或者由該等鍵結表示之基團為更佳。In addition, A ¹ is preferably a group represented by the following formula (P-1). [Chemical formula 6]

In the 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 bonding site ^{with Y 1.} In the formula (P-1), L ¹ is preferably a single bond or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group in which two or more of these are bonded, A single bond or a hydrocarbyl group, an ether bond, a carbonyl group, -NR ^N -, or a group in which two or more of these are bonded are more preferable. The above-mentioned R ^N 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 more preferable, and a hydrogen atom is particularly preferable. As the hydrocarbon group in the above L ¹ , a saturated aliphatic hydrocarbon group with 1 to 30 carbons, an aromatic hydrocarbon group with 6 to 30 carbons, or a group represented by a combination of these are preferred, and saturated aliphatic groups with 1 to 10 carbons A group hydrocarbon group, a group in which two or more hydrogen atoms are removed from a benzene ring, or a group represented by these bonds are more preferable.

In formula (P-1), A ² is vinyl, (meth)allyl, (meth)acrylamido, (meth)acrylamido, maleimido, ethylene A phenyl group, an epoxy group, an oxetanyl group or a methylol group is preferable, and a (meth)acryloyloxy group, a (meth)acrylamido group, an epoxy group or a methylol group is more preferable.

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

式（P-2）中，A² 表示聚合性基，*表示與Y¹ 的鍵結部位。 式（A-2）中，A² 與式（P-1）中之A² 的含義相同，且較佳態樣亦相同。 式（P-3）中，A² 表示聚合性基，L² 表示烴基、醚鍵、羰基、硫醚鍵、磺醯基、碳酸酯鍵、-NR^N -、或者將該等鍵結兩個以上之基團，Z¹ 表示醚鍵、酯鍵、胺甲酸乙酯鍵、脲鍵、碳酸酯鍵或醯胺鍵，*表示與Y¹ 的鍵結部位。R^N 如上所述。 式（P-3）中，A² 與式（P-1）中之A² 的含義相同，且較佳態樣亦相同。 式（P-3）中，L² 係烴基、（聚）伸烷氧基、或者由該等的組合表示之基團為較佳，烴基為更佳。 在本說明書中，（聚）伸烷氧基係指伸烷氧基或聚伸烷氧基。又，在本發明中，聚伸烷氧基係指直接鍵結兩個以上伸烷氧基之基團。聚伸烷氧基中所包含之複數個伸烷氧基中之伸烷基可以分別相同，亦可不同。當聚伸烷氧基包含伸烷基不同之複數種伸烷氧基時，聚伸烷氧基中之伸烷氧基的排列可以係無規排列，亦可以係具有嵌段之排列，還可以係具有交替等圖案之排列。 作為上述烴基，伸烷基、2價芳香族烴基、或者由該等的組合表示之基團為較佳，伸烷基為更佳。 作為上述伸烷基，碳數1～30的伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳。 在本發明中，當簡單記載為“脂肪族烴基”、“飽和脂肪族烴基”、“烷基”、“伸烷基”等時，除非另有說明，否則該等基可以具有支鏈結構及環狀結構中的至少一個。例如，除非另有說明，否則“烷基”中包括直鏈烷基、支鏈烷基、環狀烷基及由該等的組合表示之烷基。 作為上述芳香族烴基，碳數6～30的芳香族烴基為較佳，碳數6～20的芳香族烴基為更佳，伸苯基或伸萘基為進一步較佳，伸苯基為特佳。 作為上述（聚）伸烷氧基中之伸烷基，碳數2～10的伸烷基為較佳，碳數2～4的伸烷基為更佳，伸乙基或伸丙基為更佳，伸乙基為進一步較佳。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數量）為2～20為較佳，2～10為更佳，2～5為進一步較佳，2～4為特佳。 式（P-3）中，Z¹ 表示醚鍵、酯鍵、胺甲酸乙酯鍵、脲鍵或醯胺鍵為較佳，酯鍵、胺甲酸乙酯鍵、脲鍵或醯胺鍵為更佳。 在本發明中，當簡單記載為“酯鍵”、“胺甲酸乙酯鍵”、“醯胺鍵”等時，該等鍵結的朝向並不受限定。例如，當上述Z¹ 係酯鍵時，與Z¹ 中之L² 的鍵結部位可以係酯鍵中之碳原子，亦可以係氧原子。Moreover, A ¹ is preferably a group represented by the following formula (P-2) or formula (P-3). [Chemical formula 7]

In formula (P-2), A ² represents a polymerizable group, and * represents a bonding site ^{with Y 1.} Of formula (A-2), the same formula A ² (P-1) in the meaning of A ^2, and the preferred aspects are also the same. In formula (P-3), A ² represents a polymerizable group, and L ² represents a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, a carbonate bond, -NR ^N -, or two of these are bonded In the above groups, Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, a carbonate bond or an amide bond, and * represents a bonding site ^{with Y 1.} R ^{N is} as described above. Formula (P-3), the same formula A ² (P-1) in the meaning of A ^2, and the preferred aspects are also the same. In the formula (P-3), the L ² -based hydrocarbon group, (poly)alkoxyl group, or a group represented by a combination of these is preferred, and the hydrocarbon group is more preferred. In this specification, (poly)alkoxyl group refers to alkoxyl group or polyalkoxyl group. Furthermore, in the present invention, the polyalkoxyl group refers to a group to which two or more alkoxyl groups are directly bonded. The alkylene groups in the plurality of alkoxylate groups contained in the polyalkyleneoxy group may be the same or different. When the polyoxyalkylene group contains a plurality of different alkylene groups, the arrangement of the alkoxy group in the polyoxyalkylene group can be a random arrangement, a block arrangement, or It is an arrangement with alternating patterns. As the above-mentioned hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof is preferable, and an alkylene group is more preferable. As the above-mentioned alkylene group, an alkylene group having 1 to 30 carbon atoms is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred. In the present invention, when simply described as "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl", "alkylene", etc., unless otherwise specified, these groups may have a branched structure and At least one of the cyclic structures. For example, unless otherwise specified, "alkyl" includes straight-chain alkyl, branched-chain alkyl, cyclic alkyl, and alkyl groups represented by combinations of these. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred, phenylene or naphthylene is more preferred, and phenylene is particularly preferred. . As the alkylene group in the above-mentioned (poly)alkoxyl group, the alkylene group having 2 to 10 carbon atoms is preferred, the alkylene group having 2 to 4 carbon atoms is more preferred, and the ethylene or propylene group is more preferred. Preferably, ethylene is further preferred. In addition, the number of alkoxyl groups contained in the polyalkoxyl group (the number of repeating polyalkoxyl groups) is preferably from 2 to 20, more preferably from 2 to 10, and even more preferably from 2 to 5, 2～4 are particularly good. In the formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond or an amide bond is preferably, and an ester bond, a urethane bond, a urea bond or an amide bond is more preferred. good. In the present invention, when simply described as "ester bond", "urethane bond", "amide bond", etc., the orientation of these bonds is not limited. For example, when the aforementioned Z ¹ is an ester bond, the bonding site to L ^{2 in Z 1} may be a carbon atom in the ester bond or an oxygen atom.

In addition, from the viewpoint of chemical resistance, the ^{distance between the polymerizable group contained in A 1} and the main chain of the polyimide is preferably 0-15, and more preferably 0-5. Here, ^{the distance between the polymerizable group contained in A 1} and the main chain of the polyimide refers to the smallest number of atoms contained between the atom contained in the main chain of the polyimide and the polymerizable group The number. For example, in the resin represented by the formula (PA-1) in the following embodiments, the distance between the methacrylamide group and the main chain is 0, and the distance between the methacrylamide group and the main chain of the polyimide Is 1. In addition, in the resin represented by the formula (PA-3) in the following examples, the distance between the methacryloxy group bonded to the main chain by the urea bond and the main chain of the polyimide is 5. The distance between the methacryloxy group bonded to the main chain by the urethane bond and the main chain of the polyimide is 6. In addition, regarding the resin represented by the formula (PA-4) in the examples described later, the distance between the two acrylamide groups and the main chain of the polyimide is 0. That is, when the polyimide has a ring structure inside the main chain, the "atoms included in the main chain of the polyimide" includes the ring members of the ring structure. In addition, when A ¹ contains a plurality of polymerizable groups, among ^{the polymerizable groups contained in A 1} , the distance between the polymerizable group closest to the main chain and the main chain of the polyimide is preferably 0-15 , 0～5 is better. In addition, when A ¹ contains a plurality of polymerizable groups, it ^{is more preferable that the distance between all the polymerizable groups contained in A 1} and the main chain of the polyimide is 0-15, and 0-5 is particularly preferable.

-n- In the formula (1-1), n represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and 1 or 2 is Especially good, 2 is the best. In addition, when n is an integer of 2 or more, n pieces of A ¹ may be the same or different.

式（Y-1）或式（Y-2）中，L^Y1 及L^Y2 分別獨立地表示伸烷基，碳數1～10的伸烷基為較佳，碳數1～4的伸烷基為更佳，伸烷基為進一步較佳。 式（Y-3）或式（Y-4）中，L^Y4 分別獨立地表示單鍵或2價烴基，單鍵為較佳。作為2價烴基，伸烷基為較佳，碳酸1~10的伸烷基為更佳，碳酸1~4的伸烷基為進一步較佳。 式（Y-4）中，L^Y3 係單鍵或可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHC（=O）-或將該等組合兩個以上之基團為較佳，單鍵、可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-S（=O）₂ -為更佳，選自包括-CH₂ -、-O-、-S-、-S（=O）₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價基團為進一步較佳。 式（Y-3）或式（Y-4）中，n分別獨立地表示1～4的整數，1或2為較佳，1為更佳。-Y ¹ -Y ¹ represents an n+divalent organic group, and a hydrocarbon group is preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group with 1 to 30 carbons, an aromatic hydrocarbon group with 6 to 30 carbons, or a group represented by a combination of these are preferred. The saturated aliphatic hydrocarbon group with 1 to 10 carbons, from Groups in which two or more hydrogen atoms are removed from the benzene ring, or groups represented by these bonds are more preferable. As Y ¹ , for example, structures represented by the following formulas (Y-1) to (Y-4) are preferably cited. In the following formulas (Y-1) to (Y-4), * respectively represents the bonding site with the oxygen atom in the ester bond in the formula (1-1), and # respectively represents the bond with the formula (1-1) The bonding site of A ^1. [Chemical formula 8]

In the formula (Y-1) or (Y-2), L ^Y1 and L ^Y2 each independently represent an alkylene group, and an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 4 carbon atoms is preferred. To be more preferable, the alkylene group is still more preferable. In formula (Y-3) or formula (Y-4), L ^Y4 each independently represents a single bond or a divalent hydrocarbon group, and a single bond is preferred. As the divalent hydrocarbon group, an alkylene group is preferable, an alkylene group of 1 to 10 carbonic acid is more preferable, and an alkylene group of 1 to 4 carbonic acid is more preferable. In the formula (Y-4), L ^Y3 is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(= O) ₂ -, -NHC(=O)- or a combination of two or more of these groups is preferred, single bond, C1-C3 alkylene group which can be substituted by fluorine atom, -O-, -C(=O)-, -S- or -S(=O) ₂ -is more preferably, selected from -CH ₂ -, -O-, -S-, -S(=O) ₂ -,- The divalent group in the group of C(CF ₃ ) ₂ -and -C(CH ₃ ) _{2-is further preferred.} In formula (Y-3) or formula (Y-4), n each independently represents an integer of 1 to 4, 1 or 2 is preferred, and 1 is more preferred.

-Q ¹ -In the formula (1-1), Q ¹ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR ^N- At least one bonded group of is preferred. R ^{N 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. Furthermore, as the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable. As the above-mentioned 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 them, from the viewpoint of solvent solubility, Q ¹ is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and a group containing an aromatic hydrocarbon ring group is more preferable.

In addition, ^{it is preferable that Q 1} includes a polymerizable group-containing group. As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferred, and a vinyl group, (meth)allyl group, (meth)acrylamido group, (methyl) group ) Allyloxy group, maleimide group, vinyl phenyl group, epoxy group, oxetanyl group or hydroxymethyl group are more preferred, (meth)acryloyloxy group, (methyl) An acrylamide group, an epoxy group, or a methylol group is more preferable. The number of polymerizable groups contained in Q ¹ is one or more, preferably 1-15, more preferably 1-10, more preferably 1-5, particularly preferably one or two, and one is optimal. As the group containing ^{the polymerizable group in Q 1} , the group represented by the above formula (P-1) is preferred, and the group represented by the above formula (P-2) or formula (P-3) is more preferred. Preferably, the group represented by formula (P-3) is further preferred.

In addition, it is ^{preferable that Q 1} includes at least one structure selected from the group consisting of a structure represented by any one of the following formula (A-1) to the following formula (A-5), which is represented by the following formula ( A-1)-The structure represented by any one of the following formula (A-5) is more preferable.

式（A-1）～（A-5）中，R^A11 ～R^A14 、R^A21 ～R^A24 、R^A31 ～R^A38 、R^A41 ～R^A48 及R^A51 ～R^A58 分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基、鹵素原子或包含聚合性之基團，L^A31 及L^A41 分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，*分別獨立地表示與其他結構的鍵結部位。[Chemical formula 9]

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 each independently represent a hydrogen atom, An alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, a halogen atom or a polymerizable group, L ^A31 and L ^A41 each independently represent a single bond, a carbonyl group, a sulfonyl group, 2 In a saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group, or a halogenated alkylene group, * each independently represents a bonding site to another structure.

From the viewpoint of chemical resistance, among them, ^{it is preferable that Q 1 has} a structure represented by formula (A-1), formula (A-2), formula (A-3), or formula (A-4).

In the formula (A-1), R ^A11 to R ^A14 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a cyclic alkyl group having 3 to 12 carbons, an alkoxy group having 1 to 6 carbons, A hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbons, a halogen atom or a group containing a polymerizable group are preferred. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbons, and carbon An alkoxy group having 1 to 6, a halogenated alkyl group having 1 to 3 carbons, or a group containing a polymerizable group is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. As the group containing the above- ^{mentioned polymerizable group in the above-mentioned R A11} to R ^A14 , the group represented by the above-mentioned formula (P-1) is preferred, which is represented by the above-mentioned formula (P-2) or (P-3) The group is more preferable, and the group represented by formula (P-3) is still more preferable. Examples of the halogen atom or the halogen atom in the halogenated alkyl group in the above R ^A11 to R ^A14 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred.

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

In the formula (A-3), R ^A31 to R ^A38 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a cyclic alkyl group having 3 to 12 carbons, an alkoxy group having 1 to 6 carbons, A hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbons, a halogen atom or a group containing a polymerizable group are preferred. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbons, and carbon An alkoxy group having 1 to 6, a halogenated alkyl group having 1 to 3 carbons, or a group containing a polymerizable group is more preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbons are more preferable. Examples of the halogen atom or the halogen atom in the halogenated alkyl group in the above R ^A31 to R ^A38 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. As the group containing the above- ^{mentioned polymerizable group in the above-mentioned R A31} to R ^A38 , the group represented by the above-mentioned formula (P-1) is preferred, and is represented by the above-mentioned formula (P-2) or (P-3) The group is more preferable, and the group represented by formula (P-3) is still more preferable. In formula (A-3), L ^A31 represents a single bond, a divalent saturated hydrocarbon group with 1 to 6 carbons, a divalent unsaturated hydrocarbon group with 5 to 24 carbons, -O-, -S-, -NR ^N -, A heterocyclic group or a halogenated alkylene group having 1 to 6 carbon atoms is preferred, which represents a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group is preferred, and represents a single bond or -O- is Further better. The above-mentioned R ^N 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 more preferable, and a hydrogen atom is particularly preferable. The above-mentioned divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, and a divalent aromatic hydrocarbon group is preferred. As the above-mentioned heterocyclic group, for example, a group in which two hydrogen atoms are removed from an aliphatic or aromatic heterocyclic ring is preferable, and a group in which two hydrogen atoms are removed from an aliphatic or aromatic heterocyclic ring is preferable. Pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, morpholine ring, etc. in the ring structure of the group with two hydrogen atoms removed For better. The morpholine ring and the heterocyclic ring may further form a condensed ring with other heterocyclic ring or hydrocarbon ring. The number of ring members of the above heterocyclic ring is preferably 5-10, more preferably 5 or 6. In addition, as the hetero atom in the above heterocyclic group, an oxygen atom, a nitrogen atom or a sulfur atom is preferred. Examples of the halogen atom in the above-mentioned halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred.

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

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

In addition, in formulas (A-1) to (A-5), * is preferably a bonding site to the main chain of the resin independently.

In addition, from the viewpoint of the flexibility of the cured film obtained, Q ¹ in the formula (1-1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ^{0 -.} Ar ^{0 is} each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, more preferably 6-18, particularly preferably 6-10), and phenylene is preferred. L ^{0 has the same meaning as L A31} in (A-3) above, and the preferred aspects are also the same.

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

[Chemical formula 10]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, ^{and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or Trifluoromethyl, * each independently represents a bonding site with other structures.

Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). The fluorinated alkyl group and so on.

[Chemical formula 11]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. * Each independently indicates the bonding site with other structures.

式（1-3）中，X¹ 、Y¹ 、A¹ 、n及X² 分別與式（1-1）中的X¹ 、Y¹ 、A¹ 、n及X² 的含義相同，較佳態樣亦相同。 式（1-4）中，Q¹ 與式（1-1）中的Q¹ 的含義相同，較佳態樣亦相同。-Carboxylic dianhydride and diamine compound- The repeating unit represented by the formula (1-1) is derived from the carboxylic dianhydride represented by the following formula (1-3) or is represented by the following formula (1-4) The structure of the diamine compound is preferable. [Chemical formula 12]

In the formula (1-3), X ^1, in Y ^1, A ^1, n and X ² in the formula ^{(1-1) X 1, Y 1} , A 1, X ² and n and the meanings of the preferred The appearance is also the same. In the formula (1-4), the same meaning as Q ¹ and Q in the formula (1-1) is ^1, the preferred aspects are also the same.

Examples of the carboxylic dianhydride represented by the formula (1-3) include anhydrides (AA-1) to (AA-6), anhydrides (AA-8) and the like used in Examples described later. In addition, as the carboxylic dianhydride, a carboxylic dianhydride having a reactive group can be used. As said reactive group, a carboxyl group, a carboxyl halide group, a hydroxyl group, an amino group, an isocyanate group, a cyclic ether group, etc. are mentioned. After reacting a carboxylic dianhydride having a reactive group and a diamine such as a diamine represented by the formula (1-4), the above-mentioned reactive group and the group having the above-mentioned reactive group and a polymerizable group are reacted The compound reacts, thereby obtaining a resin having a repeating unit represented by formula (1-1). For example, after reacting a carboxylic dianhydride having a reactive group (carboxyl group, etc.) like the anhydride (AA-7) in the following Examples and a diamine such as a diamine represented by the formula (1-4), it is reacted with A compound having a group that reacts with the above-mentioned reactive group and a polymerizable group, such as glycidol, reacts, and thereby can also be used as a resin containing a repeating unit represented by formula (1-1).

The diamine represented by the formula (1-4) may be selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminopropane. Aminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1, 3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3, 3'-Dimethylcyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diamine Biphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenyl Phenylmethane, 4,4'-diaminodiphenyl sulfide or 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide or 3,3'-diamino Diphenyl sulfide, 4,4'-diaminobenzophenone 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-hydroxyl Phenyl) chrysene, bis(4-amino-3-hydroxyphenyl) chrysene, 4,4'-diamino p-terphenyl, 4,4'-bis(4-aminophenoxy) biphenyl, Bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(2-aminophenoxy)benzene Yl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-bis Amino diphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene Group) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4, 4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4 '-Tetraamino diphenyl ether, 1,4-diamine Anthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) sulfone, 4, 4'-Dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-( 3',5'-Diaminobenzyloxy) ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p- Phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,6-dihydroxy-1, 3-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-amine Phenyl)ethane, diaminobenzylaniline, diamine benzoic acid, ester of diamine benzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4 -Aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7- Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis [4-(4-Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene , 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl , 4,4'-bis(4-amino-2-trifluoromethylphenoxy) diphenyl sulfide, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) Diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl- 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'- At least one diamine among hexafluorotolidine and 4,4'-diaminotetraphenyl.

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

[Chemical formula 13]

[Chemical formula 14]

In addition, diamines having at least two alkylene glycol units in the main chain can also be cited as preferred examples. Preferably, it is a diamine that contains two or more of ethylene glycol chains and propylene glycol chains or both in total in one molecule, and more preferably is the above-mentioned diamine and does not contain an aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropyl) (Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., But it is not limited to these.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[Chemical formula 15]

In the above, x, y, and z are the arithmetic averages.

In addition, as the diamine compound imparting the structure of the above formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)- 4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One kind of these may be used, or two or more kinds may be used in combination.

In addition, for the purpose of improving the adhesion to the substrate, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasil can be used as the diamine component. Diamines with siloxane structure such as oxanes.

In addition, the following diamines can also be preferably used. [Chemical formula 16]

-The content of the repeating unit represented by the formula (1-1)- The content of the repeating unit represented by formula (1-1) in the specific resin is not particularly limited, but relative to the total mass of the specific resin, 10% by mass or more is preferred, 20% by mass or more is more preferred, and 30% by mass The above is further preferred. The upper limit of the above content is not particularly limited as long as it is 100% by mass or less. In addition, as an aspect of the specific resin, it is also preferable to include the repeating unit represented by the formula (1-1) in a high content. In this case, relative to the total mass of the specific resin, the content of the repeating unit represented by formula (1-1) is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. Good, more than 80% by mass is particularly good, and more than 90% by mass is the best. The upper limit of the above content is not particularly limited as long as it is 100% by mass or less. The specific resin may include one type of repeating unit represented by formula (1-1) alone, or may include two or more different structures of repeating units represented by formula (1-1). When a specific resin contains two or more different structures of repeating units represented by formula (1-1), the total content of all repeating units represented by formula (1-1) contained in the specific resin is included in the above content range The inner is better.

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

式（2-1）～（2-3）中，X¹ 、Y¹ 、A¹ 、X² 、n及Q¹ 分別與式（1-1）中的X¹ 、Y¹ 、A¹ 、X² 、n及Q¹ 的含義相同，較佳態樣亦相同。 式（2-1）～（2-3）中，A^A1 、A^A2 、R¹¹³ 及R¹¹⁴ 分別與後述式（1）中之A^A1 、A^A2 、R¹¹³ 及R¹¹⁴ 的含義相同，且較佳態樣亦相同。-A repeating unit represented by any one of formula (2-1) to formula (2-3)- As other repeating units, any of the following formulas (2-1) to (2-3) can be cited A repeating unit of representation. When the specific resin contains a repeating unit represented by any one of the following formulas (2-1) to (2-3), the specific resin includes the following formulas (2-1) to (2-3) in the main chain Any one of represents the repeating unit in the preferred. [Chemical formula 17]

In formulas (2-1) to (2-3), X ¹ , Y ¹ , A ¹ , X ² , n, and Q ¹ are respectively the same as X ¹ , Y ¹ , A ¹ , X in formula (1-1) ^2. The meanings of n and Q ¹ are the same, and the preferred aspects are also the same. In formulas (2-1) to (2-3), A ^A1 , A ^A2 , R ¹¹³ and R ¹¹⁴ have the same meanings as ^{A A1} , A ^A2 , R ¹¹³ and R ¹¹⁴ in formula (1) described later, and The preferred aspect is also the same.

＜＜Content＞＞ The total content of the repeating units represented by any one of formulas (2-1) to (2-3) in the specific resin is not particularly limited, but it is preferably 30% by mass or more relative to the total mass of the specific resin. 20% by mass or more is more preferable, and 10% by mass or more is still more preferable. The lower limit of the above total content is not particularly limited, as long as it is 0% by mass or more. In addition, from the viewpoint of the chemical resistance of the cured film obtained, as a specific resin, it is also an aspect that does not substantially contain the repeating unit represented by formula (2-1) to formula (2-3) Better. In this case, relative to the total mass of the specific resin, the total content of the repeating units represented by any one of formulas (2-1) to (2-3) is preferably 5% by mass or less, and 3% by mass or less More preferably, 1% by mass or less is still more preferable. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The specific resin may individually include one type of repeating unit represented by any one of formula (2-1) to formula (2-3), or may include two or more different structures from formula (2-1) to formula (2- 3) Any one of the repeating units. When the specific resin contains two or more different structures of the repeating unit represented by any one of formula (2-1) to formula (2-3), the specific resin contained in the specific resin consists of formula (2-1) to formula ( It is preferable that the total content of all repeating units indicated by any one of 2-3) is included in the above-mentioned content range.

式（4）中，R¹³¹ 表示2價有機基，R¹³² 表示4價有機基。-Repeating unit represented by formula (4)- The specific resin may further include a repeating unit represented by formula (4). When the specific resin includes a repeating unit represented by the following formula (4), it is preferable that the specific resin includes a repeating unit represented by the following formula (4) in the main chain. However, the repeating unit represented by the above formula (1-1) does not correspond to the repeating unit represented by the formula (4). [Chemical formula 18]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

As ^{the divalent organic group represented by R 131 , the same group as Q 1} in the formula (1-1) can be exemplified, and the preferred range is also the same.

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

[Chemical formula 19]

R ¹¹² is a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, an aromatic hydrocarbon group with 6 to 20 carbonic acid which may have a substituent, -O-, -C(=O )-, -S-, -S(=O) ₂ -, -NHC(=O)- or a combination of two or more groups are preferred, selected from single bonds, carbons that can be substituted by fluorine atoms The number of alkylene groups from 1 to 3, the phenylene group which may have substituents, the groups among -O-, -C(=O)-, -S- and -S(=O) ₂ -are more preferable, Selected from including -CH ₂ -, phenylene which may have substituents, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -C(CF ₃ ) _2- And the divalent group in the group of -C(CH ₃ ) _{2-is further preferred.} * Each independently indicates the bonding site with other structures.

式（R-1）中，X¹ 及X² 分別獨立地表示芳香族烴基或脂肪族環基，Y¹ 表示n+2價有機基，X^R1 分別獨立地表示取代基，n表示0以上的整數，*分別獨立地表示與其他結構的鍵結部位。Moreover, as R ¹³² , a tetravalent organic group represented by the following formula (R-1) is also preferably mentioned. [Chemical formula 20]

In formula (R-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, X ^R1 each independently represents a substituent, and n represents 0 or more Integer, * respectively independently indicate the bonding site with other structures.

In formula (R-1), X ¹ , X ² , Y ^{1 and n have the same meanings as X 1} , X ² , Y ¹ and n in formula (1-1), and preferred aspects are also the same. ^{However, in the description of Y 1} in formula (1-1), the ^{description of "the bonding site with A 1} in formula (1-1)" can be replaced with "X ^{R1 in formula (R-1)} Or the bonding site of the hydrogen atom".

In the formula (R-1), X ^R1 is preferably a substituent that does not include a polymerizable group each independently. As said polymerizable group, the polymerizable group demonstrated in A ¹ in said formula (1-1) can be mentioned. As the substituent not containing the above-mentioned polymerizable group, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group or a phosphonic acid group are preferred. Furthermore, from the viewpoint of alkali developability, X ^R1 is preferably a phenolic hydroxyl group, carboxyl group or sulfo group, and more preferably a carboxyl group. From the viewpoint of solvent solubility, X ^R1 is preferably an alkyl group having 1 to 10 carbons or an aromatic hydrocarbon group having 6 to 20 carbons.

^{Regarding the tetravalent organic group represented by R 132} in the formula (4), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[Chemical formula 21]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 132} in formula (4).

As a specific example of tetracarboxylic dianhydride, anhydride (AA-7), pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4' selected from the examples below can be illustrated. -Biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3 ,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-di Phenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4 '-Oxodiphthalic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride , 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4 ,5,6-Naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2, 4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3 -Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and the carbons thereof At least one of alkyl derivatives having 1 to 6 and alkoxy derivatives having 1 to 6 carbons.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples.

[Chemical formula 22]

＜＜Content＞＞ The content of the repeating unit represented by formula (4) in the specific resin is not particularly limited, but relative to the total mass of the specific resin, 90% by mass or less is preferred, 80% by mass or less is more preferably, and 70% by mass or less is Further better. The lower limit of the above total content is not particularly limited, as long as it is 0% by mass or more. In addition, from the viewpoint of the chemical resistance of the cured film obtained and the viewpoint of improving the transparency of the resin, as a specific resin, the content of the repeating unit represented by formula (4) is also low. Better. In this case, relative to the total mass of the specific resin, the total content of the repeating unit represented by formula (4) is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less , 10% by mass or less is particularly good. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The specific resin may include one type of repeating unit represented by formula (4) alone, or may include two or more different structures of repeating units represented by formula (4). When the specific resin contains two or more different structures of repeating units represented by formula (4), it is preferable that the total content of all repeating units represented by formula (4) contained in the specific resin is included in the above-mentioned content range .

式（1）中，A^A1 及A^A2 分別獨立地表示氧原子或-NH-，R¹¹¹ 表示2價有機基，R¹¹⁵ 表示4價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。 又，在由式（1）表示之重複單元中所記載之包含兩個醯胺基之結構中，其中一個可以被醯亞胺環化。 作為上述一個被醯亞胺環化之結構，可列舉下述式（1-A）或下述式（1-B）。 [化學式24]

式（1-A）或式（1-B）中，A^A1 、A^A2 、R¹¹¹ 、R¹¹⁵ 、R¹¹³ R¹¹⁴ 分別與式（1）中的，A^A1 、A^A2 、R¹¹¹ 、R¹¹⁵ 、R¹¹³ 及R¹¹⁴ 的含義相同，較佳態樣亦相同。-Repeating unit represented by formula (1)- The specific resin may further include a repeating unit represented by the following formula (1). When the specific resin contains a repeating unit represented by the following formula (1), the specific resin preferably contains a repeating unit represented by the following formula (1) in the main chain. [Chemical formula 23]

In formula (1), A ^A1 and A ^A2 each independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group. In addition, in the structure containing two amide groups described in the repeating unit represented by formula (1), one of them may be cyclized with amide. As the above-mentioned one structure which is cyclized by an imine, the following formula (1-A) or the following formula (1-B) can be mentioned. [Chemical formula 24]

In formula (1-A) or formula (1-B), A ^A1 , A ^A2 , R ¹¹¹ , R ¹¹⁵ , R ¹¹³ R ¹¹⁴ are the same as those in formula (1), A ^A1 , A ^A2 , R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ have the same meaning, and preferred aspects are also the same.

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

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

[Chemical formula 25]

In the formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, and a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ -or a (poly) alkoxy group having 4 to 30 carbons (as an alkylene group, carbon The number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repetitive number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3). Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecylene and other alkylene groups, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -is better. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylene group. In formula (III), * represents the bonding site with other structures. As a preferred embodiment, the ^{monovalent organic group of R 113} or R ¹¹⁴ in formula (1) has one, two, or three (preferably one) aliphatic groups, aromatic groups, and Aralkyl and so on. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be cited. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As the ^{monovalent organic group represented by R 113} or R ¹¹⁴ , a substituent that improves the solubility of the developer can be preferably used.

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

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

The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic ring). The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. , Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl , Dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a stilbene ring, a pentene ring, an indene ring, Azulene ring, heptene ring, indenene ring, perylene ring, fused pentabenzene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terphenylene ring, etc.) or substituted or unsubstituted Aromatic heterocyclic group (as the cyclic structure constituting the group, pyrrole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrimidine ring, and pyridine ring) , Indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, quinoline ring, naphthyridine ring, quinoline ring, quinazole Morpholine ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, chromene ring, xanthene ring, phenanthene ring, phenanthrene ring or Brown 𠯤 ring).

In formula (1), R ^{115 has the same meaning as R 132} in formula (4), and preferred aspects are also the same. In formula (1), R ^{111 has the same meaning as Q 1} in the above formula (1-1), and preferred aspects are also the same.

＜＜Content＞＞ The total content of the repeating unit represented by formula (1) in the specific resin is not particularly limited, but relative to the total mass of the specific resin, 30% by mass or less is preferred, 20% by mass or less is more preferably, and 10% by mass or less To be further preferred. The lower limit of the above total content is not particularly limited, as long as it is 0% by mass or more. Moreover, from the viewpoint of the chemical resistance of the cured film obtained, it is also preferable that the specific resin does not substantially contain the repeating unit represented by the formula (1). In this case, relative to the total mass of the specific resin, the total content of the repeating units represented by formula (1) is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less . The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The specific resin may include one type of repeating unit represented by formula (1) alone, or may include two or more different structures of repeating units represented by formula (1). When the specific resin contains two or more different structures of repeating units represented by formula (1), it is preferable that the total content of all repeating units represented by formula (1) contained in the specific resin is included in the above-mentioned content range . In addition, when the specific resin contains a repeating unit represented by formula (1-A) or formula (1-B), the repeating unit represented by formula (1), the repeating unit represented by formula (1-A), and the repeating unit represented by formula (1-A), and It is preferable that the total content of the repeating unit represented by the formula (1-B) is included in the above-mentioned content range.

-End structure- The terminal structure of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, monoamines, monohydric alcohols, phenols, mercaptans, thiophenols, acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive esters can be used. A blocking agent such as a compound to seal the end. Among these blocking agents, it is preferable to use monoamines. Preferred compounds for monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol , Furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohols such as tert-butanol and adamantanol Wait. Examples of preferable compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and the like. Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxyl -6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy -5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2 -Aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more kinds of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of kinds of blocking agents. In addition, when sealing the amine group at the end of the resin, it can be sealed with a compound having a functional group capable of reacting with the amine group. As for the preferable sealing agent for the amino group, carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc. are preferable, and carboxylic acid anhydride and carboxylic acid chlorine are more preferable. Examples of preferable compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and benzoic anhydride. In addition, preferred compounds of carboxylic acid chlorine include acetyl chloride, acrylic chloride, acryl chloride, methacrylic chloride, trimethyl acetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexyl chloride, Cinnamon chloride, 1-adamantyl carbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzyl chloride, etc.

[content] From the viewpoint of increasing the elongation at break of the cured film obtained, the content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the curable resin composition. The mass% or more is more preferable, and 40 mass% or more is more preferable. As the upper limit of the above content, from the viewpoint of improving the resolution of the curable resin composition, 99.5% by mass or less is preferable, 99% by mass or less is more preferable, 98% by mass or less is more preferable, and 97% by mass or less is It is still more preferable, and 95% by mass or less is still more preferable.

[Physical properties of specific resin] -Molecular weight- The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and even more preferably 10,000 to 100,000. The number average molecular weight (Mn) of the specific resin is preferably 800-250,000, more preferably 2,000-100,000, and still more preferably 4,000-50,000. In addition, a preferred aspect of the present invention includes an aspect in which a specific resin having a large molecular weight is used. According to the above aspect, a cured film with excellent film strength can be obtained. Regarding the Mw of the specific resin used in the above embodiment, 40,000 or more is preferable, 50,000 or more is more preferable, 60,000 or more is more preferable, 70,000 or more is particularly preferable, and 80,000 or more is most preferable. The upper limit of Mw is not particularly limited, but it is preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less. In addition, with regard to the Mn of the specific resin used in the above embodiment, 10,000 or more is preferable, 15,000 or more is more preferable, 18,000 or more is more preferable, 20,000 or more is particularly preferable, and 25,000 or more is most preferable. The upper limit of Mn is not particularly limited, but it is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. Regarding the degree of dispersion of the molecular weight of the specific resin, 1.5 to 3.5 are preferable, and 2 to 3 are more preferable. In this specification, the degree of molecular weight dispersion refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

-Acid Value- When the curable resin composition is used for the solvent development described later, the acid value of the specific resin is preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, and more preferably 0.3 mmol/g. The lower limit of the above acid value is not particularly limited, as long as it is 0 mmol/g or more. 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, and even more preferably 2 to 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 a base having a pH of 12 or higher (for example, sodium hydroxide). In addition, the acid group preferably has a pKa of 10 or less. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. The above-mentioned acid group is contained in the specific resin, for example, Q ¹ in the repeating unit represented by formula (1-1), X ^R1 in the repeating unit represented by formula (4), and in the repeating unit represented by formula (4) The R ¹³¹ and so on. As said acid group, a phenolic hydroxyl group, a carboxyl group, a sulfo group, etc. are mentioned, A carboxyl group is preferable.

-Polymerizable base value- The molar amount of the polymerizable group contained in 1g of the specific resin (polymerizable base value, unit is gol/g) is preferably 0.05-10 mol/g, more preferably 0.1-6 mol/g . ^{The polymerizable group includes, for example, A 1} and Q ¹ in the repeating unit represented by formula (1-1) ^{, R 131} in the repeating unit represented by formula (4), and the like. When the specific resin contains ethylenically unsaturated bonds as the polymerizable group, the molar amount of the ethylenically unsaturated bonds contained in 1 g of the specific resin is preferably 0.05-10 mol/g, and more preferably 0.1-6 mol/g. When the specific resin contains a polymerizable group such as a cyclic ether group and a methylol group as the polymerizable group, the molar amount of the polymerizable group contained in 1 g of the specific resin is preferably 0.05-10 mol/g, 0.1-6 mol/g g is better.

-Imidation rate (ring-closing rate)- The imidization rate (ring-closing rate) of the specific resin is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The upper limit of the above-mentioned imidization rate is not particularly limited as long as it is 100% or less. The said imidization rate is measured by the following method, for example. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 in the vicinity ^{of 1377 cm-1} , which is an absorption peak derived from the imine structure, was determined. Next, after the polyimide was heat-treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 in the vicinity of ^{1377 cm -1 was obtained.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be obtained based on the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

-Fluorine atomic weight-From the viewpoint of the film strength of the cured film obtained, it is preferable that the specific resin has a fluorine atom. The fluorine atom weight relative to the total mass of the specific resin is preferably 1-50 mol/g, and more preferably 5-30 mol/g. ^{For example, the fluorine atom contained in Q 1} in the repeating unit represented by formula (1-1), R ¹³² in the repeating unit represented by formula (4), or R ¹³¹ in the repeating unit represented by formula (4) is ^{Preferably, it is contained in Q 1} in the repeating unit represented by formula (1-1), R ¹³² in the repeating unit represented by formula (4), or R ¹³¹ in the repeating unit represented by formula (4) It is more preferable as a fluorinated alkyl group.

[Specific example] As a specific example of a specific resin, the specific resin used in the Example mentioned later can be mentioned.

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

Specifically, the manufacturing method of the resin used in the present invention preferably includes the following process: a process of reacting a tetravalent carboxylic acid compound and a diamine compound to obtain a polyimide precursor (precursor manufacturing process); and The process of making the above-mentioned polyimide precursor imidization (imidization process).

-Precursor manufacturing process- In the precursor manufacturing process, a polyimide precursor is obtained by reacting a tetravalent carboxylic acid compound and a diamine compound. The above-mentioned polyimine precursor is preferably a polyimine precursor containing a repeating unit represented by the above formula (2-3). In addition, the polyimide precursor may include a repeating unit represented by the above formula (1) in addition to the repeating unit represented by the formula (2-3). The above-mentioned tetravalent carboxylic acid compound may be a carboxylic acid derivative modified by esterification or halogenation of at least one of the four carboxylic acids, or a carboxylic dianhydride or carboxylic dianhydride in which two carboxylic acids have been anhydride separately For better. As the carboxylic dianhydride, specifically, the carboxylic dianhydride represented by the above formula (1-3) or the carboxylic dianhydride represented by the above formula (7) can be used. In addition, as the tetravalent carboxylic acid compound, a compound having a structure in which the carboxylic dianhydride is hydrolyzed, or a compound having a structure in which the compound is modified such as esterification or halogenation can be used. As said diamine compound, the diamine compound represented by the said formula (1-4) can be used specifically,. In addition, the production of the precursor can be performed with reference to a known method.

-Imidation process- In the imidization process, the polyimide precursor obtained in the precursor manufacturing process is imidized to obtain a specific resin. The imidization process can be thermal imidization (for example, heat-based imidization), chemical imidization (for example, imidization using a catalyst), and a combination of these. Any one of the imidization is performed by heating, for example, in the presence of a catalyst such as an amine compound. In addition, in the imidization process, for example, a dehydrating agent can be used. As a dehydrating agent, carboxylic anhydride, such as acetic anhydride, etc. are mentioned. In the production of the specific resin of the present invention, the heating temperature can be set to a low temperature (for example, 80°C to 150°C, etc.) for imidization. Therefore, from the viewpoint of energy saving, the method for producing the specific resin of the present invention Also useful. In addition, the details of the imidization can be performed by a known method.

-Other processes- The method for producing the resin of the present invention preferably further includes the following process: compound A having at least two hydroxyl groups and at least one reactive group, and a compound having a group capable of forming a bond with the above-mentioned reactive group and a polymerizable group B reaction to obtain a diol compound (diol manufacturing process); and react the above diol compound with a compound having 3 carboxyl groups or a derivative of the above 3 carboxyl compound to obtain two ester bonds The manufacturing process of tetravalent carboxylic acid compound (the manufacturing process of tetravalent carboxylic acid compound). Through these processes, the carboxylic dianhydride represented by the above formula (1-3) can be obtained. In the aforementioned precursor production process, as the tetravalent carboxylic acid compound, a tetravalent carboxylic acid compound having the above two ester bonds is preferably used.

<<Diol production process>> The reactive group in the compound A used in the diol production process is not particularly limited, and examples thereof include an amino group, a hydroxyl group, and a carboxyl group. The group capable of bonding to the reactive group in the compound B is not particularly limited, and examples thereof include a hydroxyl group, a carboxylic acid group, a carboxylic acid halide group, an epoxy group, and an isocyanate group. Examples of the polymerizable group in the compound B include the groups exemplified as the group included ^{in A 1 in the above formula (1-1).} The diol production process is implemented by performing the following processes (1) to (3), for example. (1) A process in which the two hydroxyl groups contained in compound A are protected by well-known protecting groups (for example, acetal protecting groups, ether protecting groups, acetal protecting groups, silyl ether protecting groups, etc.) (2) The process of introducing the polymerizable group into the reactive group in compound A and the group that can form a bond with the reactive group in compound B. (3) The process of deprotecting the above-mentioned protective group. Reactions in each process The conditions and the like may be appropriately determined with reference to known reaction conditions and the like. Specifically, the process of synthetic intermediate (AA) in the following examples corresponds to (1) above, the process of synthetic intermediate (AB) corresponds to (2), and the process of synthetic intermediate (AC) corresponds to the above (3).

＜Production process of tetravalent carboxylic acid compound＞＞ In the tetravalent carboxylic acid compound production process, the diol compound obtained in the above-mentioned diol production process is reacted with a compound having 3 carboxyl groups or a derivative of the above-mentioned compound having 3 carboxyl groups, thereby obtaining an ester having two Bonded tetravalent carboxylic acid compound. Examples of the above-mentioned compound having 3 carboxyl groups or derivatives of the above-mentioned compound having 3 carboxyl groups include compounds having 3 carboxyl groups, compounds having one carboxyl group and one carboxylic acid anhydride group, compounds having one carboxylic acid halide group and one carboxyl group. Compounds with acid anhydride groups, compounds with one carboxylic acid ester group and one carboxylic acid anhydride group, compounds with three carboxylic acid ester groups, compounds with one carboxylic acid halide group and two carboxylic acid ester groups, etc., but with one A compound of a carboxylic acid halide group and a carboxylic acid anhydride group is preferred. The conditions of the above-mentioned reaction and the like may be appropriately determined with reference to a known esterification reaction. Specifically, in the following examples, the process of synthesizing anhydride (AA-1) from the intermediate (A-C) and trimellitic anhydride chloride corresponds to the process of producing the tetravalent carboxylic acid compound described above.

-Other manufacturing methods- In addition, the method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by heating and dehydrating at a high temperature when the carboxylic dianhydride and the diamine compound are reacted. As a carboxylic dianhydride, the carboxylic dianhydride represented by Formula (1-3) is mentioned, for example. The carboxylic dianhydride represented by the above formula (1-3) is preferably a compound obtained in the above-mentioned tetravalent carboxylic acid compound production process. As the diamine compound, the diamine compound represented by the above formula (1-4) can be used. In addition, the method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by decarburizing at a high temperature during the reaction of the carboxylic dianhydride and the diisocyanate compound. As a carboxylic dianhydride, the carboxylic dianhydride represented by Formula (1-3) is mentioned, for example. The carboxylic dianhydride represented by the above formula (1-3) is preferably a compound obtained in the above-mentioned tetravalent carboxylic acid compound production process. As the diisocyanate compound, a compound in which two amine groups in the compound represented by the above formula (1-4) are respectively changed to an isocyanate group can be mentioned. For the details of these production methods, reference can be made to a known synthetic method of polyimide.

In addition, the method for producing the resin used in the present invention may be the following production method, which includes: a process of reacting a tetravalent carboxylic acid compound having a reactive group with a diamine compound to obtain a polyimide precursor; A process for the imidization of the precursor of imidamine to obtain a resin with a reactive group; and a process for reacting the above resin with a compound C having a group capable of forming a bond with the above reactive group and a polymerizable group.

It does not specifically limit as said reactive group, but an amino group, a hydroxyl group, a carboxyl group, etc. are mentioned. The tetravalent carboxylic acid compound having the above-mentioned reactive group can be a carboxylic acid derivative modified by esterification or halogenation of at least one of the four carboxylic acids, or it can be a carboxylic dianhydride in which two carboxylic acids are separately anhydride , Carboxylic dianhydride is preferred. As the carboxylic dianhydride having the above-mentioned reactive group, specifically, the carboxylic dianhydride having a reactive group among the carboxylic dianhydrides represented by the above-mentioned formula (7) can be used. In addition, as the tetravalent carboxylic acid compound, a compound having a structure in which the carboxylic dianhydride is hydrolyzed, or a compound having a structure in which the compound is modified such as esterification or halogenation can be used. In addition, a carboxylic dianhydride having no reactive group may be used in combination. As said diamine compound, the diamine compound represented by the said formula (1-4) can be used specifically,.

The group capable of bonding to the above-mentioned compound C reactive group is not particularly limited, and examples thereof include a hydroxyl group, a carboxylic acid group, a carboxylic acid halide group, an epoxy group, and an isocyanate group. Examples of the polymerizable group in the above compound C include the groups exemplified as the polymerizable group contained in A ¹ in the above formula (1-1).

In addition, the method for producing the resin used in the present invention may be a production method comprising: reacting a compound having 3 carboxyl groups or a derivative of the above-mentioned compound having 3 carboxyl groups with a diamine compound or a diisocyanate compound to obtain The process of producing a compound D of two amide ring structures and two carboxylic acids; and a process of reacting the above-mentioned compound D with a diol compound having a polymerizable group to obtain a resin.

Examples of the above-mentioned compound having 3 carboxyl groups or derivatives of the above-mentioned compound having 3 carboxyl groups include compounds having 3 carboxyl groups, compounds having one carboxyl group and one carboxylic acid anhydride group, compounds having one carboxylic acid halide group and one carboxyl group. Compounds with acid anhydride groups, compounds with one carboxylic acid ester group and one carboxylic acid anhydride group, compounds with three carboxylic acid ester groups, compounds with one carboxylic acid halide group and two carboxylic acid ester groups, etc., but with one A compound of a carboxyl group and a carboxylic anhydride group is preferred. As said diamine compound, the diamine compound represented by the said formula (1-4) can be used specifically,. Specific examples of the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (1-4) are changed to isocyanate groups. The conditions and the like of the above-mentioned reaction may be appropriately determined with reference to a known imidization reaction.

式（DO-1）中，Y¹ 、A¹ 及n分別與式（1-1）中的Y¹ 、A¹ 及n的含義相同，較佳態樣亦相同。 又，可以併用不具有聚合性基之其他二醇化合物。 得到上述樹脂之製程中之反應條件參考公知的聚酯的製造方法適當決定即可。As the diol compound having the above-mentioned polymerizable group, a compound represented by the following formula (DO-1) can be mentioned. [Chemical formula 26]

In formula (DO-1), Y ¹ , A ^{1 and n have the same meanings as Y 1} , A ¹ and n in formula (1-1), and preferred aspects are also the same. In addition, other diol compounds that do not have a polymerizable group may be used in combination. The reaction conditions in the process for obtaining the above-mentioned resin may be appropriately determined with reference to a known polyester production method.

As an example, the following shows a synthesis scheme when a resin having the same structure as the polyimide (PA-1) in the examples is obtained by the above-mentioned manufacturing method. [Chemical formula 27]

＜Solvent＞ The curable resin composition of the present invention contains a solvent. As the solvent, any known solvent can be used. Solvent-based organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfenes, amines, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, alkoxy Ethyl ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) ), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy Ethyl-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, Ethyl Caproate, Ethyl Conate, Dimethyl malonate, diethyl malonate and the like are preferable.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene two Alcohol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. are preferable.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucanone, and dihydrodextran. Ketones and the like are preferable.

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

As the sulfenites, for example, dimethyl sulfenite is preferable.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide , N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. are preferred By. Examples of 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 monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol Monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether , Methyl benzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., a form in which two or more of them are mixed is also preferable.

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferred. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

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 more preferably is 5 to 75% by mass. The amount is more preferably 10 to 70% by mass, more preferably 20 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 two or more types. When two or more solvents are contained, the total amount is preferably within the above-mentioned range.

＜Other resins＞ The curable resin composition of the present invention may also include other resins different from the above-mentioned specific resins (hereinafter, also simply referred to as "other resins"). Examples of other resins include polyimides, polyimide precursors, polyimide imines, polyimide imine precursors, polysiloxanes, and silicone structures that are different from specific resins. The resin, epoxy resin, acrylic resin, etc. For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, or a cured film having excellent chemical resistance can be obtained. For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, an acrylic resin with a high polymerizable base value having a weight average molecular weight of 20,000 or less is added to the composition, thereby improving the coating properties of the composition. The chemical resistance of the cured film, etc.

〔Polyimide, polyimide (other resins)〕 From the viewpoint of the film strength of the cured film to be obtained, it is preferable that polyimide or polyimide, which is another resin, have a repeating unit represented by the above formula (4). In the polyimide or polyimide, the repeating unit represented by the formula (4) may be one type or two or more types. Moreover, in addition to the repeating unit of the above formula (4), the polyimide or polyimide may include other types of repeating units. For example, it is preferable that polyamidoimines further include repeating units containing an amide structure or repeating units containing an amide structure and an amide structure.

As an embodiment of the polyimide or polyimide imide of the present invention, 50 mol% or more of the total repeating unit can be exemplified, furthermore 70 mol% or more, especially 90 mol% or more, as the formula ( 4) The polyimide precursor of the repeating unit indicated. As the upper limit, it is actually 100 mol% or less.

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

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

For example, by heating etc., the polyimide precursor or the polyimide imine precursor which is the other resin mentioned later is cyclized, and the polyimide or polyimide imide is obtained.

〔Polyimide precursors, polyimide imine precursors (other resins)] From the viewpoint of the film strength of the cured film obtained, the polyimide precursor or the polyimide precursor preferably has a repeating unit represented by the above formula (1).

In the polyimide precursor or polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. In addition, structural isomers of the repeating unit represented by formula (1) may also be included. Furthermore, in addition to the repeating unit of the above formula (1), the polyimide precursor or the polyimide precursor may also include other types of repeating units. For example, it is preferable that the polyamide imine precursor further includes a repeating unit containing an amide structure or a repeating unit containing an amide structure and a carboxylate structure.

As an embodiment of the polyimide precursor or polyimide precursor in the present invention, 50 mol% or more of the total repeating unit can be exemplified, and then 70 mol% or more, especially 90 mol% The above is the polyimide precursor of the repeating unit represented by formula (1). As the upper limit, it is actually 100 mol% or less.

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

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

The polyimide precursor or polyimide imine precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, after halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, it is obtained by reacting it with a diamine.

In the production method of the polyimide precursor or the polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one type or two or more types.

The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When manufacturing polyimide precursors or polyimide imine precursors, a process that includes precipitation of solids is preferred. Specifically, the polyimide precursor or polyimide precursor in the reaction solution is precipitated in water and dissolved in tetrahydrofuran or the like to dissolve the polyimide precursor or polyimide precursor The solvent of the precursor can precipitate solids.

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

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

[Photopolymerization initiator] The curable resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can also be an active agent that has some effect with a light-excited sensitizer to generate active free radicals.

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

As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, and hexaarylbisimidazole , Oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, amino acetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, thiophene Metal compounds, organoboron compounds, iron arene complexes, etc. For the details, refer to the descriptions of 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, Paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated in this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and the content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one aspect of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphonium oxide-based initiator described in Japanese Patent No. 4225898 can be used.

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

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

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 having an absorption maximum wavelength matched with a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF SE), which are commercially available products, can be used.

As the metallocene compound, IRGACURE-784 (manufactured by BASF SE) and the like can be exemplified.

As the photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, 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 functions as a photohardening accelerator.

As specific examples of the oxime compound, the compounds described in Japanese Patent Application Publication No. 2001-233842, the compounds described in Japanese Patent Application Publication No. 2000-080068, and the compounds described in Japanese Patent Application Publication No. 2006-342166 can be used. .

As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-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 >C=N-O-C(=O)- in the molecule.

[Chemical formula 28]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF SE), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japan Special Publication 2012- The photo-radical polymerization initiator described in 014052 No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

An oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) and the like described in paragraph 0101 of the 2013-164471 Bulletin.

As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779, or oximes having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl triketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group including trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one compound in the group is more preferable, a metallocene compound or an oxime compound is more preferable, and an oxime compound is still more preferable.

In addition, the photoradical polymerization initiator can also use benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings. Quinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used.

[Chemical formula 29]

In the formula (I), R ^I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, a phenyl group or C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, carbon interrupted by one or more oxygen atoms A phenyl or biphenyl group substituted with at least one of an alkyl group having ^{2-18 and} an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II), or the same group as ^{R I00} Groups, R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen.

[Chemical formula 30]

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

In addition, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

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

[Thermal polymerization initiator] The curable resin composition of the present invention may also include a thermal polymerization initiator as a polymerization initiator, and in particular, may include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can also proceed in the heating process described later, and therefore 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 2008-063554 A.

When a thermal polymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5- 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above-mentioned range.

＜Polymerizable compound＞ [Free radical polymerizable compound] The curable resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of radical polymerizable groups include groups having ethylenically unsaturated bonds, such as vinyl groups, allyl groups, vinyl phenyl groups, and (meth)acrylic groups. The radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferable.

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

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and 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 more radically polymerizable compound containing two or more radically polymerizable groups, and at least one trifunctional or more functionally free radical polymerizable compound. A base polymerizable compound is more preferable. In addition, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher radical polymerizable compound. For example, the number of functional groups of a bifunctional or more polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amides Types, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amine groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogens Substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as sulfonyl groups or toluene sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can also be used. As a specific example, the description in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated in this specification.

In addition, a radically polymerizable compound having a boiling point of 100°C or higher under normal pressure is also preferable. As examples, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentyl erythritol tri(meth)acrylate can be cited. Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohol Compounds that are (meth)acrylated after addition of ethylene oxide or propylene oxide, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193. (Meth) urethane acrylates described in the gazette, and polyester acrylates described in each gazette of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490 Types, epoxy acrylates and other polyfunctional acrylates or methacrylates as the reaction product of epoxy resin and (meth)acrylic acid, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. Moreover, the polyfunctional (meth)acrylate etc. which are made to react the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, and a polyfunctional carboxylic acid are mentioned.

In addition, as a preferable radical polymerizable compound other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. It is a compound or cardo resin with two or more groups containing ethylenically unsaturated bonds.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Application Publication No. 2015-034964, the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these The content is compiled into this manual.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radically polymerizable compounds, which are added to polyfunctional alcohols. Ethylene oxide or propylene oxide is then (meth)acrylated compound.

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

As a radically polymerizable compound, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

Commercial products of radically polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having four ethyleneoxy chains, and SR-494 as a bifunctional acrylate having four ethyleneoxy chains. SR-209, 231, 239 manufactured by Sartomer Company, Inc. of methyl acrylate, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with six pentyloxy chains, as having 3 isoforms TPA-330 of trifunctional acrylate of butoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., Ltd.), NK ester M-40G, NK ester 4G , NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a radically polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Urethane acrylates, 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 have epoxy resins described in Urethane compounds with an ethane-based skeleton are also preferred. Furthermore, as the radically polymerizable compound, those described in JP 63-277653, JP 63-260909, and 01-105238 having an amino group in the molecule can also be used. Structure or sulfide structure compound.

The radical polymerizable compound may also be a radical polymerizable compound having an acid group such as a carboxyl group and 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 the non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have the freedom of an acid group A base polymerizable compound is more preferable. Particularly preferably, the non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Among the radically polymerizable compounds, the aliphatic polyhydroxy compound is one of neopentylerythritol or dineopentaerythritol. Compound. As a commercially available product, as a polyacid modified acrylic oligomer manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. are mentioned, for example.

The preferred acid value of the radically polymerizable compound having an acid group is 0.1-40 mgKOH/g, and particularly preferably 5-30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above range, the workability in production is excellent, and the developability is also excellent. In addition, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of the resolution of the pattern and the stretchability of the film, it is preferable to use a bifunctional methacrylate or acrylate for the curable resin composition of the present invention. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene Glycol diacrylate and polyethylene glycol chain formula weight is about 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polytetrafluoroethylene Ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol Diacrylate, 1,6 hexanediol dimethacrylate, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (epoxy) of bisphenol A Ethane) adduct diacrylate, EO adduct metal ester of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct metal ester of bisphenol A , 2 hydroxy-3-acryloxy propyl propyl ester, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, 2 with other urethane bonds Functional acrylate, difunctional methacrylate with urethane bond. These can mix and use 2 or more types as needed. From the viewpoint of suppressing warpage accompanying the control of the elastic coefficient of the cured film, the curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth)acrylic acid Derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether, etc. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. In addition, the curable resin composition of the present invention can also contain allyl compounds such as diallyl phthalate and triallyl trimellitate as a bifunctional or more radically polymerizable compound.

A polymerizable compound may be used individually by 1 type, and may mix and use 2 or more types. When two or more are used at the same time, the total amount is preferably within the above-mentioned range.

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

[Photo Acid Generator] The curable resin composition of the present invention preferably contains a photoacid generator. By containing the photoacid generator, for example, acid is generated in the exposed part of the curable resin composition layer, so that the solubility of the exposed part in the developer (for example, an alkaline aqueous solution) is increased, and the exposed part can be developed. Positive relief pattern for liquid removal. In addition, the following aspect may also be adopted: the curable resin composition contains a photoacid generator and an acid crosslinking agent described later, for example, the crosslinking reaction of the thermal crosslinking agent is promoted by the acid generated in the exposed part, and the exposed part It is less likely to be removed by the developer than the non-exposed area. According to this aspect, a negative relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates acid by exposure, but it can be exemplified by onium salt compounds such as quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, and phosphonium salts, and phosphonium salts. Sulfonate compounds such as imine sulfonate, oxime sulfonate, diazo disulfonate, disulfonate, o-nitrobenzyl sulfonate, etc.

As the quinonediazide compound, sulfonic acid ester of quinonediazide is bonded to polyhydroxy compound, sulfonamide of quinonediazide is bonded to polyamine compound, and sulfonic acid of quinonediazide. Those bonded to a polyhydroxypolyamine compound by at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional group of the polyhydroxy compound or polyamine compound be substituted by quinonediazide.

In the present invention, as the quinonediazide, at least one of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl can be preferably used. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonate compound extends to the g-ray region of the mercury lamp, which is suitable for g-ray exposure. In the present invention, it is preferable to select the 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound according to the exposure wavelength. In addition, the naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group may be contained in the same molecule, and 4-naphthoquinone diazide sulfonyl ester compound may also be contained in the same molecule. Azosulfonate compound and 5-naphthoquinone diazide sulfonate compound.

The naphthoquinonediazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, or it can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the above-mentioned naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, etc. Compound salt or ester compound, etc.

As the onium salt compound or the sulfonate compound, the compounds described in paragraphs 0064 to 0122 of JP 2008-013646 A, etc. can be cited. Moreover, as a photoacid generator, a commercial item can be used. As commercially available products, WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all Fujifilm Corporation and Wako Pure Chemical Industries, Ltd.), etc.

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

[Hot Acid Generator] The curable resin composition of the present invention may also contain a thermal acid generator. The thermal acid generator has the ability to generate acid by heating and promotes selected from the group consisting of compounds having methylol, alkoxymethyl or oxymethyl, epoxy compounds, oxetane compounds, and benzophenone compounds At least one of the compounds or the effect of the crosslinking reaction of the methylol contained in the specific resin. Moreover, when the curable resin composition of the present invention contains a thermal acid generator, it is preferable that the specific resin contains an epoxy group and a methylol group as the 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. In addition, if a thermal acid generator is selected as a thermal acid generator, the curing resin composition is applied to the substrate and then dried (pre-baking: about 70 to 140°C), which does not generate acid, but is patterned by subsequent exposure and development. In the final heating (curing: about 100 to 400°C) that is performed after conversion, acid is generated, which can suppress the decrease in sensitivity during development, which is preferable. Regarding the thermal decomposition start temperature, when the thermal acid generator is heated in a pressure-resistant capsule to 500°C at 5°C/min, it is determined as the peak temperature of the heat generation peak with the lowest temperature. As a device used when measuring the start temperature of thermal decomposition, Q2000 (manufactured by TA Instruments.) can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, such as aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluoromethanesulfonic acid Haloalkanesulfonic acids and the like are preferred. As an example of such a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.

Among them, from the viewpoint of leaving little residue in the cured film and not easily degrading the physical properties of the cured film, it is more preferable to produce alkanesulfonic acid with 1 to 4 carbon atoms or haloalkanesulfonic acid with 1 to 4 carbon atoms, as the thermal acid Producer, methanesulfonic acid (4-hydroxyphenyl) dimethyl sulfonate, methanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonate, benzyl methanesulfonate ( 4-Hydroxyphenyl)methylsulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonate, methanesulfonate (4-hydroxyphenyl)methyl( (2-Methylphenyl)methyl)silium salt, trifluoromethanesulfonic acid (4-hydroxyphenyl)dimethylsilium salt, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy) Phenyl) dimethyl sulfonate, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methyl sulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl ) Methyl sulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonate, 3-(5-(((propanesulfonyl)oxy ) Imino) thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexa Fluoropropane.

In addition, as the thermal acid generator, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the specific resin, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, and therefore the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the 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 more preferable.

＜Acid crosslinking agent＞ The photocurable resin composition of the present invention preferably contains an acid crosslinking agent. In the present invention, the acid cross-linking agent is preferably a compound having a plurality of groups in the molecule that promote the cross-linking reaction by the action of acid. As the acid crosslinking agent, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group is directly bonded to a nitrogen atom is more preferred. As an acid crosslinking agent, for example, a compound having the following structure can be cited: reacting amine-containing compounds such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., with formaldehyde or formaldehyde and alcohol, and reacting from methylol or Alkoxymethyl is substituted for the hydrogen atom of the above-mentioned amino group. The production method of these compounds is not particularly limited, as long as they have the same structure as the compound produced by the above-mentioned method. In addition, it may be an oligomer in which the methylol groups of these compounds are self-condensed with each other. As the above-mentioned amine-containing compound, the crosslinking agent using melamine is referred to as melamine-based crosslinking agent, the crosslinking agent using glycoluril, urea or alkylene urea is referred to as urea-based crosslinking agent, and the crosslinking agent using melamine The crosslinking agent of alkyl urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among them, the photocurable resin composition of the present invention preferably includes at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent. At least one compound in the group of melamine-based crosslinking agents is more preferred, and it is even more preferred to include a glycoluril-based crosslinking agent.

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

As specific examples of the urea-based crosslinking agent, for example, monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, monomethoxyl Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril Alkylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethyl glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril Glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylglycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril Urea and other glycoluril crosslinking agents; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Crosslinking of methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea Agent Monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxy Allyl urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc. Coupling agent; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole Pyridone and so on.

As specific examples of the benzoguanamine-based crosslinking agent, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolform Alkylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine; Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxy Methyl benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethyl Benzoguanamine, monobutoxymethyl benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine Guanamine and so on.

In addition, as the compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it is also preferable to use at least one selected from the group consisting of hydroxymethyl and alkoxymethyl. A compound in which a radical is directly bonded to an aromatic ring (preferably a benzene ring). As specific examples of such compounds, benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diethylene glycol monophenyl ether, Bis (hydroxymethyl) benzophenone, hydroxymethyl phenyl hydroxymethyl benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) Benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diethylene glycol monophenyl ether, bis(methoxymethyl) Methyl) benzophenone, methoxymethyl benzyloxy methyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4 ,4'.4''-ethylene tri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl ) Ethylene] bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4 '-Diol etc.

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

In addition, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzophenone compounds as the acid crosslinking agent.

[Epoxy compound (compound with epoxy group)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes cross-linking reaction below 200°C, and does not cause dehydration reaction from cross-linking, so it is difficult to cause film shrinkage. Therefore, containing the epoxy compound is effective for suppressing the low-temperature curing and warpage of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the coefficient of elasticity is further reduced, and furthermore, it is possible to suppress warpage. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include double A type epoxy resin; double F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butane Alkylene glycol type epoxy resin or polyol hydrocarbon type epoxy resin such as glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether; polypropylene glycol diglycidyl ether Polyalkylene glycol type epoxy resin such as ether; epoxy-containing polysiloxane such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to this. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700 , EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) ) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (Registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above are Product name, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA Corporation), CELLOXIDE2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, GT401, EPOLEAD ( Registered trademarks) PB4700, EPOLEAD (registered trademarks) PB3600SERVINUS B0134, B0177 (the above are product names, manufactured by DAI-CELL-ALLNEX Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH -75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S , EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxetane compound (compound with oxetanyl group)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, and 1,4-bis{[ (3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzene Dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester and the like. As a specific example, ARON OXETANE series manufactured by TOAGOSEI CO., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, which can be used alone or in combination of two or more use.

[Benzo 㗁 𠯤 compound (compound with benzo azole group)] The benzoglyph compound does not produce outgassing during hardening due to the cross-linking reaction derived from the ring-opening addition reaction, and further reduces heat shrinkage to suppress the generation of warpage, so it is preferable.

As a preferable example of the benzo 㗁 𠯤 compound, can cite Ba type benzo 㗁 𠯤, Bm type benzo 㗁 𠯤, Pd type benzo 㗁 𠯤, Fa type benzo 㗁 𠯤, (the above is the product name, Shikoku Chemicals Corporation), polyhydroxystyrene resin benzox adducts, novolak-type dihydrobenzox compounds. These are used alone, or two or more of them may be mixed.

The content of the acid crosslinking agent relative to the total solid content of the curable resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, more preferably 0.5-15% by mass, and 1.0 ~10% by mass is particularly preferred. The acid crosslinking agent may contain only one type or two or more types. When two or more acid crosslinking agents are contained, the total amount thereof is preferably within the above-mentioned range.

＜Compounds with sulfonamide structure, compounds with thiourea＞ From the viewpoint of improving the adhesion of the obtained cured film to the substrate, the curable resin composition of the present invention further includes at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having thiourea Compounds are preferred.

式（S-1）中，R表示氫原子或有機基，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中之R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以係具有兩個以上磺醯胺結構之化合物，但是具有一個磺醯胺結構之化合物為較佳。[Compound with sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 31]

In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * each independently represents a bonding site to another structure. The above-mentioned R is preferably the same group as ^{R 2} in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferred.

式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基，R¹ 、R² 及R³ 中的兩個以上可以彼此鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地係1價有機基為較佳。 作為R¹ 、R² 及R³ 的示例，可列舉氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合兩個以上之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可列舉甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為環烷基，例如，可列舉環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可列舉甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基甲矽烷基，碳數1～10的烷氧基甲矽烷基為較佳，碳數1～4的烷氧基甲矽烷基為更佳。作為上述烷氧基甲矽烷基，可列舉甲氧基甲矽烷基、乙氧基甲矽烷基、丙氧基甲矽烷基及丁氧基甲矽烷基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。又，上述芳基可以具有烷基等取代基。作為上述芳基，可列舉苯基、甲苯基、二甲苯基及萘基等。 作為雜環基，可列舉從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、二氫吡喃環及四氫吡喃環、三𠯤環等雜環結構中去除一個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 32]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ may be bonded to each other to form a ring structure. Preferably, R ¹ , R ² and R ³ are each independently a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aromatic group. Base ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. In addition, the above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, pyridine ring , Pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropyran ring, tetrahydropyran ring, trihydropyran ring and other heterocyclic structures with one hydrogen atom removed Groups and so on.

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

As examples of compounds having a sulfonamide structure, benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, and p-toluenesulfonamide can be cited. Amide, hydroxynaphthalene sulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzene sulfonamide, p-chlorobenzene sulfonamide, methane sulfonamide, N,N-di Methylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonate Amido, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基，R⁴ 及R⁵ 可以鍵結而形成環結構，R⁴ 可以與鍵結有*之其他結構鍵結而形成環結構，R⁵ 可以與鍵結有*之其他結構而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound with Thiourea] Thiourea is a structure represented by the following formula (T-1). [Chemical formula 33]

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ can be bonded to form a ring structure, and R ⁴ can be bonded to other structures with * It forms a ring structure, and R ⁵ can be bonded to other structures with * to form a ring structure, and * each independently represents a bonding site with other structures.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl ether group. , Carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more groups. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. In addition, the above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, pyridine ring , Pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropyran ring, tetrahydropyran ring, trihydropyran ring and other heterocyclic structures with one hydrogen atom removed Groups and so on. The compound having thiourea may be a compound having two thioureas, but a compound having one thiourea is preferred.

式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或一價有機基，R⁴ ～R⁷ 中的至少兩個可以彼此鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 34]

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, ^{and at least two of R 4} to R ⁷ may be bonded to each other to form a ring structure.

Formula (T-2), the same as R (T-1) and R ⁴ and R ⁵ in the formula the meanings of R ⁵ and ^4, the preferred aspects are also the same. In the formula (T-2), it ^{is preferable that R 6} and R ⁷ are each independently a monovalent organic group. In formula (T-2), ^{the preferred aspect of the monovalent organic group in R 6} and R ⁷ is the same as the preferred aspect of the monovalent organic group in R ⁴ and R ⁵ in formula (T-1) the same.

Examples of compounds having thiourea include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantane Thiourea, N-benzylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diiso Propylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea , N,N-diphenylthiourea, ethylene thiourea (2-imidazoline thione), carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

[content] Relative to the total mass of the cured resin composition of the present invention, the total content of the compound having a sulfamide structure and the compound having a thiourea structure is preferably 0.05-10% by mass, and more preferably 0.1-5% by mass. 0.2 to 3% by mass is more preferable. The curable resin composition of the present invention may include only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having thiourea, or two or more types. At present, when one type is included, the content of the compound is preferably within the above-mentioned range, and when two or more types are included, the total amount thereof is preferably within the above-mentioned range.

＜Onium salt＞ The curable resin composition of the present invention preferably contains an onium salt. In particular, when a polyimide precursor is included as the other resin, the curable resin composition preferably includes an onium salt. The type of onium salt and the like are not particularly limited, and preferably ammonium salt, imine salt, sulphur salt, iodonium salt or phosphonium salt is mentioned. Among them, from the viewpoint of high thermal stability, an ammonium salt or an imine salt is preferable, and from the viewpoint of compatibility with a polymer, a sulfonium salt, an phosphonium salt, or a phosphonium salt is preferable.

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

The onium salt used in the present invention may be a thermal base generator. The thermal base generator refers to a compound that generates a base by heating, and for example, an acidic compound that generates a base when heated to 40° C. or more can be cited.

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

式（101）中，R¹ ～R⁴ 分別獨立地表示氫原子或烴基，R¹ ～R⁴ 中的至少兩個可以分別鍵結而形成環。-Ammonium cation- As the ammonium cation, a fourth ammonium cation is preferred. In addition, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 35]

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 formula (101), R ¹ to R ⁴ are each independently a hydrocarbon group preferably, an alkyl group or an aryl group is more preferable, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable . R ¹ to R ⁴ may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. When ^{at least two of R 1} to R ⁴ are bonded to each other to form a ring, the ring may include a hetero atom. As said hetero atom, a nitrogen atom can be mentioned.

The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2). [Chemical formula 36]

In Formula (Y1-1) and (Y1-2), R ¹⁰¹ represents a n-valent organic group, R ¹ is the same as in the formula (101) R ¹ have the meaning, Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n Represents an integer of 1 or more. In the formula (Y1-1), R ¹⁰¹ is preferably a group that removes n hydrogen atoms from aliphatic hydrocarbons, aromatic hydrocarbons, or structures formed by these bonds, preferably from saturated fats with 2-30 carbons Group hydrocarbon, benzene or naphthalene is more preferably a group with n hydrogen atoms removed. In formula (Y1-1), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, and a phenyl group is more preferable.

-Anion- As the anion in the ammonium salt, one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion is preferred. In view of the stability and thermal decomposition of the salt, the carboxylate anion is more preferred. good. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability, and developability of the curable resin composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the curable resin composition can be further improved.

式（X1）中，EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [Chemical formula 37]

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

In this embodiment, the electron withdrawing group refers to the one whose Hammett substituent constant σm refers to a positive value. Among them, σm is described in detail in Tono Yufu, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ C(=O) group (σm=0.63), HC≡C group (σm=0.21), CH ₂ = CH base (σm=0.06), Ac base (σm=0.38), MeOC (=O) base (σm=0.37), MeC (=O) CH=CH base (σm=0.21), PhC (=O) base ( σm=0.34), H ₂ NC (=O) CH ₂ base (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group. (Following, the same).

式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 38]

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

式（XA）中，L¹⁰ 表示單鍵或選自包括伸烷基、伸烯基、芳香族基、-NR^X -及該等的組合之群組中之2價連接基，R^X 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical formula 39]

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of alkylene, alkenylene, aromatic, -NR ^X -and combinations thereof, R ^X represents hydrogen Atom, alkyl, alkenyl or aryl.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion.

From the viewpoints that the specific resin is easily cyclized at 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 contains the pKa of a conjugate acid as an anion ( Anions having a pKaH) of 2.5 or less are preferred, and anions having a pKaH) of 1.8 or less are more preferred. The lower limit of the above-mentioned pKa is not particularly limited. From the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific resin or the like is improved, -3 or more is preferable, and -2 or more is more preferable. As the above pKa, you can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Edited: Braude, EA, Nachod, FC; Academic Press, New York, 1955 ) Or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated by the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.

As specific examples of the ammonium salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 40]

[Imine salt] In the present invention, imine salt refers to a salt of imine cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-Imine cation- As the imine cation, pyridinium cation is preferred. Moreover, as the imine cation, a cation represented by the following formula (102) is also preferable. [Chemical formula 41]

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 may be bonded to each other to form a ring. In formula (102), R ⁵ and R ^{6 have the same meanings as R 1} to R ⁴ in the above formula (101), and preferred aspects are also the same. In the formula (102), it ^{is preferable that R 7 is} bonded to at least one of R ⁵ and R ^{6 to form a ring.} The aforementioned ring may also contain heteroatoms. As said hetero atom, a nitrogen atom can be mentioned. In addition, as the above-mentioned ring, a pyridine ring is preferred.

式（Y1-3）～（Y1-5）中，R¹⁰¹ 表示n價有機基，R⁵ 與式（102）中之R⁵ 的含義相同，R⁷ 與式（102）中之R⁷ 的含義相同，n表示1以上的整數，m表示0以上的整數。 式（Y1-3）中，R¹⁰¹ 為從脂肪族烴、芳香族烴或由該等鍵結而成之結構去除n個氫原子之基團為較佳，從碳數2～30的飽和脂肪族烴、苯或萘去除n個氫原子之基團為更佳。 式（Y1-3）中，n為1～4為較佳，1或2為更佳，1為進一步較佳。 式（Y1-5）中，m為0～4為較佳，1或2為更佳，1為進一步較佳。The imine cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical formula 42]

In formulas (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same meaning as R ⁵ in formula (102), and R ^{7 has} the ^{same meaning as R 7 in formula (102)} Similarly, n represents an integer of 1 or more, and m represents an integer of 0 or more. In formula (Y1-3), R ¹⁰¹ is preferably a group that removes n hydrogen atoms from aliphatic hydrocarbons, aromatic hydrocarbons, or structures formed by these bonds, and is preferably a saturated fat with 2-30 carbons. Group hydrocarbon, benzene or naphthalene is more preferably a group with n hydrogen atoms removed. In the formula (Y1-3), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In formula (Y1-5), m is preferably from 0 to 4, 1 or 2 is more preferably, and 1 is even more preferably.

As specific examples of the imine salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 43]

[Salt] In the present invention, a sulfonium salt refers to a salt of sulfonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-Alium cation- As the alumnium cation, the third alumnium cation is preferred, and the triaryl alumnium cation is more preferred. Moreover, as a cation, a cation represented by the following formula (103) is preferable. [Chemical formula 44]

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group. R ⁸ to R ¹⁰ are each independently an alkyl group or an aryl group, preferably, an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R ⁸ to R ¹⁰ may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

[Salt] In the present invention, iodonium salt refers to a salt of iodonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-Iiodonium cation- As the iodonium cation, a diaryl iodonium cation is preferred. In addition, as the iodonium cation, a cation represented by the following formula (104) is preferred. [Chemical formula 45]

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group. It ^{is preferable that R 11} and R ¹² are independently an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R ¹¹ and R ¹² may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ¹¹ and R ¹² may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

[Phosphonium salt] In the present invention, phosphonium salt refers to a salt of phosphonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-Phosphonium cation- As the phosphonium cation, a fourth phosphonium cation is preferred, and tetraalkyl phosphonium cations, triaryl monoalkyl phosphonium cations and the like can be mentioned. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 46]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group. It ^{is preferable that R 13} to R ¹⁶ are independently an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R ¹³ to R ¹⁶ may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

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 relative 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, more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, and may be 5% by mass or less or 4% by mass or less. One type or two or more types of onium salts can be used. When two or more are used, the total amount is preferably within the above range.

<Thermal base generator> The curable resin composition of the present invention may contain a thermal base generator. In particular, when the curable resin composition contains a polyimide precursor as the other resin, the curable resin composition preferably contains a thermal alkali generator. The thermal base generator may be a compound conforming to the onium salt described above, or may be a thermal base generator other than the onium salt described above. Examples of other hot alkali generators include nonionic hot alkali generators. Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2). [Chemical formula 47]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a third amine structure, a halogen atom, or a hydrogen atom. Among them, Rb ¹ and Rb ² do not simultaneously become hydrogen atoms. Moreover, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, the third amine structure refers to a structure in which all three bonding bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amido group together with a nitrogen atom, it is not limited to this.

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 contain a cyclic structure. The cyclic structure may be any one of a monocyclic ring and a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. A single ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic cyclohexane ring and benzene ring are preferred, and the cyclohexane ring is more preferred.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferably, and 3-12 is more preferably), alkenyl (carbon number 2-24 Is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred) or aralkyl The group (the carbon number is preferably 7-25, 7-19 is more preferable, and 7-12 is still more preferable) is preferable. These groups may have a substituent in the range which exhibits the effect of this invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups which may have substituents (1-24 carbon atoms are preferred, 2-18 are more preferred, and 3-12 are further preferred). Preferably, the cycloalkyl group that may have a substituent (the carbon number is preferably 3-24, more preferably 3-18, and even more preferably 3-12) is more preferable, and the cyclohexyl group that may have a substituent is more preferable. good.

Examples of Rb ³ include alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is even more preferable), and aryl groups (the carbon number is preferably 6-22, and 6-18 is More preferably, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl (carbon number 7-23 is Preferably, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (carbon number 8-24 is preferred, 8-20 is more preferred, 8-16 is further preferred), alkoxy Group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), aryloxy group (the carbon number is 6-22 is preferable, 6-18 is more preferable, 6-12 is more preferable) Is further preferred) or aralkyloxy (the carbon number is preferably 7 to 23, 7 to 19 is more preferred, and 7 to 12 is even more preferred). Among them, cycloalkyl (3 to 24 carbon atoms is preferred, 3 to 18 is more preferred, and 3 to 12 is more preferred), aralkenyl, and aralkoxy are preferred. ^{Rb 3} may further have a substituent as long as the effect of the present invention is exerted.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 48]

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

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (the carbon number is preferably 1 to 12, and 1 to 8 is more preferable, and 1 to 3 is more preferable), and an alkenyl group (the carbon number is 2 to 12 is more preferable). Preferably, 2-8 is more preferable, 2-3 is more preferable), aryl (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), aralkyl ( The carbon number is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom.

Rb ³⁵ is an alkyl group (the carbon number is preferably 1-24, 1-12 is more preferable, and 3-8 is even more preferable), alkenyl (the carbon number is preferably 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aryl is preferred.

Furthermore, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 49]

Rb ¹¹ and Rb ^{12 is} of the formula (B1-1) in the same meaning as Rb ¹¹ and Rb ^{12 is} a. Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are more preferred), alkenyl groups (carbon number 2 to 12 are preferred, 2 ～6 is more preferable, 2～3 are more preferable), aryl group (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), aralkyl group (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl is preferred. Rb ¹⁷ is an alkyl group (the carbon number is preferably 1 to 24, 1 to 12 is more preferable, and 3 to 8 is more preferable), alkenyl group (the carbon number is 2 to 12 is preferable, and 2 to 10 is more preferable, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), of which aryl is preferred.

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

[化學式51]

Among the above-mentioned onium salts, the following compounds can be cited as specific examples of compounds as thermal base generators or other specific examples of thermal base generators. [Chemical formula 50]

[Chemical formula 51]

[Chemical formula 52]

The content of the thermal base generator is preferably 0.1 to 50% by mass relative 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 more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably within the above range.

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

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring). Ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-pyran ring, 6H-pyran ring, tricyclic ring) compound, thiourea Classes and compounds with sulfhydryl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. -059656 The compound described in paragraph 0052 of JP 2012-194520 A, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219 Compound etc.

As specific examples of migration inhibitors, the following compounds can be cited.

[Chemical formula 53]

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the curable resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass % Is more preferable.

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

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

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, p-tert-butylcatechol are preferably used , 1,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4 -Methyl-6-tertiary butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid , 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso -N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxyl )-2,6-Dimethylbenzyl)-1,3,5-tris -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6 -Tetramethylpiperidine 1-oxygen radical, phenothiazine , 1,1-diphenyl-2-pyrrole hydrazine, copper dibutyl dithiocarbonate (II), nitrobenzene, N-nitroso -N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Chemical formula 54]

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor can be, for example, 0.01 to 20.0% by mass relative to the total solid content of the curable resin composition of the present invention, 0.01 to 5 Mass% is more preferable, 0.02 to 3 mass% is more preferable, and 0.05 to 2.5 mass% is still more preferable. In addition, when the storage stability of the composition is required, the aspect of 0.02 to 15.0 mass% is also preferably cited. In this case, it is more preferably 0.05 to 10.0 mass%.

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

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

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

作為其他矽烷偶聯劑，例如，可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1,3-二甲基-丁烯）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基甲矽烷基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基琥珀酸酐。該等能夠單獨使用一種，或者組合使用兩種以上。[Chemical formula 55]

As other silane coupling agents, for example, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-epoxypropylene Oxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropoxy Propyl triethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2 -(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butene)propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and sulfides described in paragraphs 0032 to 043 of JP 2013-072935 can also be used. Department of compounds.

〔Aluminum series adhesive additives〕 As an aluminum-based adhesive agent, for example, aluminum tris(acetate ethyl acetate) aluminum, tris(acetacetone) aluminum, ethyl acetate ethyl diisopropoxide aluminum, and the like can be cited.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the specific resin, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass. By setting it to more than the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes better, and by setting it below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. There may be only one type of metal adhesion improver, or two or more types. When two or more are used, the total amount is preferably within the above-mentioned range.

＜Other additives＞ The curable resin composition of the present invention can be blended with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening touch Medium, filler, antioxidant, ultraviolet absorber, aggregation inhibitor, etc. 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 have a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator cause chemical changes to decompose, and generate free radicals, acids, or alkalis. Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone series, Michler's ketone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, sub Benzyl series, oxacyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothionine series, pyrrolopyrazole azomethine series, pyrrolopyrazole azomethine series, phthalocyanine series Series, benzopyran pyran series, indigo series and other compounds. For example, Michler’s ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzene)cyclopentane, 2,6- Bis(4'-diethylaminobenzene)cyclohexanone, 2,6-bis(4'-diethylaminobenzene)-4-methylcyclohexanone, 4,4'-bis(dimethyl Amino) chalcone, 4,4'-bis(diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indan Ketone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene) benzothiazole, 2-(p-dimethylamine Phenylvinylidene) isonaphthiazole, 1,3-bis(4'-dimethylaminophenyl)acetone, 1,3-bis(4'-diethylaminophenyl)acetone, 3,3 '-Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Bean, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p Tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl ester, diethylaminobenzoic acid isoamyl ester, 2-mercaptobenzimidazole, 1-Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzene Thiazole, 2-(p-dimethylamino styryl) naphthalene (1,2-d) thiazole, 2-(p-dimethylamino styryl) styrene, diphenyl acetamide, Benzoaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc. Moreover, as a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and this content is incorporated in this specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the curable resin composition of the present invention is preferably 0.01-20% by mass, and more preferably 0.1-15% by mass. Preferably, 0.5 to 10% by mass is more preferable. One kind of sensitizer may be used alone, or two or more kinds may be used at the same time.

[Chain Transfer Agent] The curable resin composition of the present invention may have a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a _{group of compounds having -SS-, -SO 2} -S-, -NO-, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer: Reversible Addition Fragmentation Chain Transfer: Fragmentation chain transfer) used in polymerization of dithiobenzoic acid esters, trithiocarbonic acid esters, dithiocarbamate, xanthate compounds, etc. having a thiocarbonylthio group. These low-activity free radicals are supplied with hydrogen to generate free radicals, or they can be deprotonated to generate free radicals after oxidation. In particular, thiol compounds can be preferably used.

In addition, 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 preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention, preferably 1-10 parts by mass Parts are more preferable, and 1 to 5 parts by mass are still more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total amount is preferably within the above-mentioned range.

又，界面活性劑還能夠使用國際公開第2015/199219號的0159～0165段中所記載的化合物。[Surfactant] From the viewpoint of further improving coatability, various surfactants may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the repeating number of each repeating unit. [Chemical formula 56]

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

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.005 to 1.0 mass% %. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total amount is preferably within the above-mentioned range.

[Higher fatty acid derivatives] In order to prevent the polymerization inhibition caused by oxygen, the curable resin composition of the present invention can also be added with higher fatty acid derivatives such as behenic acid or behenic acid amide, so that it can be used in the drying process after coating. Partially on the surface of the curable resin composition.

In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When there are two or more higher fatty acid derivatives, the total amount is preferably within the above range.

＜Restrictions on other contained substances＞ From the viewpoint of coating surface properties, 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 more preferably less than 0.6% by mass.

From the viewpoint of insulation, 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 less than 0.5 mass ppm. Further better. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total amount of these metals is preferably within the above-mentioned range.

In addition, as a method of reducing the metal impurities accidentally contained in the curable resin composition of the present invention, the following method can be cited: as a raw material constituting the curable resin composition of the present invention, a raw material with a small metal content is selected; The raw material of the curable resin composition of the present invention is filtered by a filter; the device is lined with polytetrafluoroethylene, etc., so that the distillation can be carried out under the condition of preventing pollution as much as possible.

Considering the use as a semiconductor material and from the perspective of wiring corrosion, 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 less than 200 mass ppm. ppm is more preferable. Among them, less than 5 mass ppm is preferable in the state of halogen ions, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion each fall within the above-mentioned range.

As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as a container, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure for the purpose of preventing impurities from mixing into the raw material or the curable resin composition. . As such a container, for example, the container described in JP 2015-123351 A can be cited.

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

In addition, for the purpose of removing foreign matter such as dust or particles in the curable resin composition, it is preferable to perform filtration using a filter. The pore diameter of the filter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filtering process of the filter, multiple filters can also be used in series or in parallel. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed by pressurization, the pressurized pressure may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.3 MPa or less is more preferable. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<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. Furthermore, in addition to this, it can also be used for formation of an insulating film of a semiconductor device, formation of a stress buffer film, and the like.

(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminate, the semiconductor device, and the manufacturing method thereof will be described.

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

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as 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. In addition, the laminate of the present invention includes two or more cured films, and it is preferable to include a metal layer between any of the above-mentioned cured films. For example, a laminated body including at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are sequentially laminated can be preferably cited. The first cured film and the second cured film are both cured films of the present invention. For example, preferably, the first cured film and the second cured film are formed by curing the curable resin composition of the present invention. The state of the film. The curable resin composition of the present invention for forming the first cured film and the curable resin composition of the present invention for forming the second cured film may have the same composition or different compositions From the viewpoint of manufacturing suitability, a composition having the same composition is preferable. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

Examples of the fields to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or a case where a pattern is formed by etching the insulating film used for packaging purposes as described above can be cited. For these applications, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masami/Supervisor, CMC Technical Library "Polyimide Materials Fundamentals and Development" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

In addition, the cured film of the present invention can also be used in the manufacture of offset printing plates or screen plates, the use of etching and forming components, and the production of protective paints and dielectric layers in electronics, especially microelectronics.

The production method of the cured film of the present invention (hereinafter, also simply referred to as "the production method of the present invention".) preferably includes a film formation process of applying the curable resin composition of the present invention to a substrate to form a film. Furthermore, it is more preferable that the method for producing a cured film of the present invention includes the film forming process described above, and further includes an exposure process of exposing the film and a developing process of developing the film (developing the film). Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming process (and the above-mentioned development process as necessary), and further includes a heating process of heating the above-mentioned film at 50-450°C. Specifically, the manufacturing process including the following (a) to (d) is also preferable. (A) Film formation process of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (B) Exposure process for exposing the film after the film formation process (C) The development process of developing the exposed film (D) Heating process of heating the developed film at 50～450℃ By heating in the above heating process, the curable resin composition layer after development can be further cured. In this heating process, for example, the above-mentioned hot alkali generator is decomposed, and sufficient curability can be obtained.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminate of this embodiment follows the above-mentioned method of manufacturing a cured film. After the cured film is formed, the process of (a) or the processes of (a) to (c) or the processes of (a) to (d) are performed again. Process. In particular, it is preferable to perform the above-mentioned processes a plurality of times in sequence, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the upper surface of the part where the cured film is provided, between the cured films, or at the two positions. In addition, in the production of the laminate, it is not necessary to repeat all the processes of (a) to (d), and it is possible to perform at least (a), preferably (a) to (c) or (a) to multiple times as described above. The process of (d) obtains a laminated body of a cured film.

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

The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and steam. Coating, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates and mold resin substrates are more preferred. In addition, as the base material, for example, a plate-shaped base material (substrate) is used.

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

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

Specifically, as the applicable method, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, and the spin coating method can be exemplified. Method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, the spin coating method, the slit coating method, the spray method, and the inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. For round substrates such as wafers, spin coating, spray coating, and inkjet methods are preferred. For rectangular substrates, slits Coating method, spraying method, inkjet method, etc. are preferable. In the case of the spin coating method, for example, a rotation speed of 300 to 3,500 rpm is applied for 10 to 180 seconds, and a rotation speed of 500 to 2,000 rpm (revolutions per minute: revolutions per minute) is applied for about 10 seconds to 1 minute. In addition, in order to obtain the uniformity of the film thickness, it is also possible to combine a plurality of rotation speeds for coating. In addition, it is also possible to apply a method of transferring a coating film formed by applying the above-mentioned applying method on a pseudo support in advance to a substrate. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used in the present invention. .

＜Drying process＞ The manufacturing method of the present invention may also include a process of drying in order to remove the solvent after forming the above-mentioned film (curable resin composition layer), followed by a film forming process (layer forming process). The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of solvent in the composition is large, vacuum drying and heat drying can also be combined. A hot plate, a hot-air oven, etc. are used for heating and drying, and there is no particular limitation.

<Exposure Process> The manufacturing method of the present invention may also include an exposure process of exposing the above-mentioned film (curable resin composition layer). As long as the amount of exposure can be cured curable resin composition is not particularly limited, for example, under an exposure energy in terms of wavelength of 365nm is irradiated 100 ~ 10,000mJ / cm ² is preferred, irradiation of 200 ~ 8,000mJ / cm ² is more preferably .

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

Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) second harmonic of YAG laser 532nm, third harmonic 355nm, etc. Regarding the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained. In addition, from the viewpoint of processing and productivity, a wide (3 wavelengths of g, h, and i rays) light source for a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

＜Development process＞ The manufacturing method of the present invention may also include a development process of developing the exposed film (curable resin composition layer). By developing, for example, in the case of a negative photosensitive resin composition, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, a development method such as a liquid coating method, spraying, dipping, and ultrasonic can be adopted.

The development is performed using a developer. The developer is not particularly limited and can be used if the curable resin composition of the present invention is a negative type curable resin composition, and the unexposed part (non-exposed part) is removed, if the curable resin composition of the present invention is a positive type curable resin composition. The curable resin composition removes the exposed part (exposed part). In the present invention, the case of using an alkaline developer as the developer is referred to as alkaline development, and the case of using a developer containing 50% by mass or more of an organic solvent as the developer is referred to as solvent development.

In alkaline development, the content of the organic solvent in the developer relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 1% by mass or less, and no organic solvent is included. Especially good. The developer in alkaline development is preferably an aqueous solution with a pH of 9-14. As the alkaline compound contained in the developer in alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, partial Sodium silicate, potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, hydrogen Tetramethylammonium oxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Among them, metal-free basic compounds are preferred, and ammonium compounds are more preferred. The basic compound may be only one type or two or more types. When there are two or more basic compounds, the total amount is preferably within the above range.

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

Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid can be preferably cited. Ethyl, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Esters, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g. 3-methoxy propionate methyl Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate)), 2-Alkoxy-2-Methyl Propionate and 2 -Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example Preferably, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as Ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons For example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, etc. are preferably used. As the sulfenes, dimethylsulfene is preferably used.

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

In addition, a surfactant may be contained in the developer.

It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developer during development is not particularly limited, and it can usually be performed at 20 to 40°C.

It can be further rinsed after the treatment with developer. In the case of solvent development, it is better to use an organic solvent different from the developer for rinsing. For example, propylene glycol monomethyl ether acetate can be cited. Preferably, the rinsing time is 5 seconds to 5 minutes. In addition, between development and processing, a process of applying both developer and processing liquid can be included. The rinsing time is preferably 1 second to 5 minutes. In the case of alkaline development, it is better to rinse with pure water. The rinsing time is preferably 5 seconds to 1 minute.

＜Heating process＞ The manufacturing method of the present invention preferably includes a process (heating process) in which the developed film is heated at 50 to 450°C. It is preferable to include a heating process after the film forming process (layer forming process), drying process, and developing process. The curable resin composition of the present invention contains polymerizable compounds other than the specific resin, but it is possible to cause unreacted polymerizable compounds other than the specific resin to undergo a curing reaction and to make the unreacted polymerizable groups in the specific resin in this process. Carry out hardening reaction and so on. In addition, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal alkali generator, during the heating process, for example, the thermal alkali generator is decomposed, thereby generating alkali and allowing the polyimide precursor to proceed. Cyclization reaction. As the heating temperature (maximum heating temperature) of the layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is further preferred, 150°C or higher is particularly preferred, and 160°C or higher is more preferred. More preferably, 170°C or higher is most preferred. As the upper limit, 450°C or lower is preferred, 350°C or lower is more preferred, 250°C or lower is more preferred, and 220°C or lower is particularly preferred.

Regarding heating, it is preferable to perform the heating rate from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1-12°C/min, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the temperature increase rate to 1°C/min or more, productivity can be ensured and excessive volatilization of amine can be prevented. By setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be alleviated.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at the beginning of the process of heating to the highest heating temperature. For example, when the curable resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition It’s better to start to warm up gradually.

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

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, it is preferable to heat at a heating temperature of 180°C to 320°C, and more preferably to heat at 180°C to 260°C. Although the reason is uncertain, it is thought that the reason is that by setting the temperature at this temperature, the polymerizable groups in the specific resin between the layers undergo a crosslinking reaction with each other.

Heating can be carried out in stages. As an example, it is possible to perform pre-heating from 25°C to 180°C at 3°C/min, and holding at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, and holding at 200°C for 120 minutes. Processing process. The heating temperature of the pretreatment process is preferably 100 to 200°C, more preferably 110 to 190°C, and further preferably 120 to 185°C. In this pretreatment process, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. Through these pretreatment processes, the characteristics of the film can be improved. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more step. For example, the pretreatment process 1 may be performed in the range of 100-150°C, and then the pretreatment process 2 may be performed in the range of 150-200°C.

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

The heating process is performed in a low oxygen concentration environment by filling in a vacuum filled with inert gases such as nitrogen, helium, argon, etc., which is preferable in terms of preventing decomposition of a specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

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

The metal layer is not particularly limited, and existing metal types can be used. Examples of copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, copper and aluminum are more preferable, and copper is still more preferable.

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

As for the thickness of the metal layer, the thickest part is preferably 0.1-50 μm, more preferably 1-10 μm.

＜Layer Process＞ Preferably, the manufacturing method of the present invention further includes a build-up process.

The build-up process includes on the surface of the cured film (resin layer) or the metal layer, and again in sequence (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process One of the series of manufacturing processes. Among them, it may be a mode in which only (a) the film forming process is repeated. In addition, it can also be set as (d) a state in which the heating process is performed collectively at the end or in the middle of the build-up. That is, it can also be set as a mode in which the processes of (a) to (c) are repeated a predetermined number of times, and then the heating of (d) is performed, thereby collectively curing the laminated curable resin composition layers. In addition, after (c) the development process, (e) the metal layer forming process may be included. In this case, the heating of (d) may be performed every time, or the heating of (d) may be collectively performed after a predetermined number of laminations. Needless to say, the layering process may further include the above-mentioned drying process and heating process as appropriate.

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

The above-mentioned layering process is preferably carried out 2 to 5 times, and it is more preferable to carry out 3 to 5 times.

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

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition in such a manner that the metal layer is further covered after the metal layer is provided. Specifically, it can be exemplified by repeating (a) film forming process, (b) exposure process, (c) developing process, (e) metal layer forming process, (d) heating process in sequence, or repeating in sequence ( a) Film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process in the end or in the middle. By alternately performing the laminating process of laminating the curable resin composition layer (resin layer) and the metal layer forming process, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 and FIG. 1 Records, and these contents are incorporated into this manual.

式（1-1）中，X¹ 及X² 分別獨立地表示芳香族烴基或脂肪族環基，Y¹ 表示n+2價有機基，A¹ 表示包含聚合性基之基團，n表示1以上的整數，Q¹ 表示2價連接基。(Resin) Furthermore, the resin of the present invention preferably has a repeating unit represented by the following formula (1-1). [Chemical formula 57]

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group.

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

＜Use＞ The resin of the present invention is preferably used as the resin contained in the curable resin composition. Moreover, for example, in a composition using a conventional polyimide, such as a composition for an interlayer insulating film, a part or all of the conventional polyimide can be replaced with the resin of the present invention without particular limitation. Since the resin of the present invention is excellent in chemical resistance, it is considered that the resin of the present invention is preferably used in, for example, a composition for forming an insulating film, a composition for forming a laminate, etc., for applications requiring chemical resistance. The composition.

[Manufacturing method of resin] The method for producing the resin of the present invention is a method for producing the resin of the present invention, which includes: making a compound A having at least two hydroxyl groups and at least one reactive group and a group capable of forming a bond with the above-mentioned reactive group, and The polymerizable compound B reacts to obtain a diol compound (diol manufacturing process); the above diol compound is reacted with a compound having 3 carboxyl groups or a derivative of the above 3 carboxyl compound to obtain Process for producing a tetravalent carboxylic acid compound with two ester bonds (manufacturing process for tetravalent carboxylic acid compound); process for reacting the above tetravalent carboxylic acid compound with a diamine compound to obtain a polyimide precursor (precursor manufacturing process) ; And the process of making the above-mentioned polyimide precursor imidization (imidization process). The detailed content of each of the above processes is as described in the manufacturing method of the specific resin, and the preferred aspects are also the same. [Example]

Hereinafter, the present invention will be further described in detail by way of examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, unless otherwise specified, "parts" and "%" are quality standards.

(Synthesis of specific resin) <Synthesis of intermediate AA> In a flask equipped with a condenser and a stirrer, add 2-amino-2-(hydroxymethylethyl)-1.3-propanediol (Tokyo Chemical Industry Co., Ltd.) 48.5 g (0.4 mol) was mixed with 240 mL of acetone, and after cooling to 0°C, 39.2 g of methanesulfonic acid (manufactured by Fujifilm Corporation and Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour ( 0.41 mol). Next, 62.5 g (0.6 mol) of 2,2-dimethoxypropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at 25°C for 3 hours. The precipitate was filtered, washed with 500 mL of acetone, and the filtrate was recovered. This was vacuum dried to obtain 99.0 g of intermediate (AA). The intermediate (AA) was confirmed from the NMR spectrum. The intermediate (AA) was ^{analyzed based on 1} H-NMR. The results are shown below. ¹ H-NMR data (heavy DMSO, 400MHz, internal standard: tetramethylsilane) δ (ppm) = 1.39 (s, 6H), 2.31 (s, 3H), 3.48-3.50 (d, 2H), 3.64-3.67 (D, 2H), 3.88-3.91 (d, 2H), 5.46-5.49 (t, 1H), 8.03 (s, 3H)

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

<Synthesis of Intermediate AC> In an eggplant-shaped flask, 13.4 g (0.45 mol) of intermediate (AB) was dissolved in 150 mL of acetonitrile, and 4.0 g of water and acid resin DOWEX (50W×40 200-400Mesh) (Aldrich) were added. , CO. LTD.) 2.5g, and stirred at 30°C for 6 hours. 20.0 g of magnesium sulfate was added thereto, and after stirring for 10 minutes, it was filtered with filter paper and concentrated with an evaporator to obtain 10.5 g of intermediate (AC). The intermediate (AC) was confirmed from the NMR spectrum. The intermediate (AC) was ^{analyzed based on 1} H-NMR. The results are shown below. ¹ H-NMR data (heavy DMSO, 400MHz, internal standard: tetramethylsilane) δ (ppm)=1.83 (s, 3H), 1.87 (s, 3H), 3.64-3.66 (d, 4H), 4.33 (s , 2H), 4.89-4.92 (t, 2H), 5.33 (s, 1H), 5.58 (s, 1H), 5.66 (s, 1H), 6.03 (s, 1H), 6.99 (s, 1H)

<Synthesis of anhydride (AA-1～AA-7)> Dissolve 18.5 g (0.88 mol) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in a flask equipped with a condenser and a stirrer In 80.8g ethyl acetate, and cool to below -10°C. Next, 10.2 g (0.04 mol) of intermediate (AC) and 7.12 g (0.09 mol) of pyridine were dissolved in 34.6 g of ethyl acetate, and they were added dropwise over 1 hour. After the dropwise addition, it was stirred at a temperature of -10°C or lower for 1 hour and at 25°C for 2 hours. Next, while filtering the reaction solution with filter paper, it was transferred to a separatory funnel, diluted with 700 mL of ethyl acetate, washed with 300 mL of water, washed twice with 200 mL of saturated sodium bicarbonate aqueous solution, and with 200 mL of aqueous hydrochloric acid and saturated salt. The water was cleaned. This was dried with magnesium sulfate, and after concentration with an evaporator, the ethyl acetate solution was crystallized in hexane. This was filtered and vacuum-dried, and the anhydride 21.0g (AA-1) was obtained. The anhydride (AA-1) was confirmed from the NMR spectrum. The anhydride (AA-1) was ^{analyzed based on 1} H-NMR. The results are shown below. ¹ H-NMR data (heavy chloroform, 400MHz, internal standard: tetramethylsilane) δ (ppm) = 1.95-1.96 (d, 6H), 4.72 (s, 2H), 4.96-5.02 (q, 4H), 5.45 (S, 1H), 5.67 (s, 1H), 5.74 (s, 1H), 6.16 (s, 1H), 6.72 (s, 1H), 8.13-8.15 (d, 2H), 8.55-8.59 (m, 4H) ) In the same way, anhydrides (AA-2) to (AA-8) of the following structures were synthesized.

[化學式59]

[Chemical formula 58]

[Chemical formula 59]

<Synthesis of polyester polyimide resin (PA-1)> In a flask equipped with a condenser and a stirrer, while removing water, 15.1 g (25 millimoles) of anhydride (AA-1), 2, 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 4.91 g (24.5 millimoles) of 4,4'-diaminodiethylene glycol monophenyl ether was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 80°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-1). The molecular weight of PA-1 is Mw=82,100 and Mn=32,500. It is estimated that the structure of PA-1 is represented by the following formula (PA-1). [Chemical formula 60]

<Synthesis of polyester polyimide resin (PA-2)> In a flask equipped with a condenser and a stirrer, while removing water, add 14.4 g (25 millimoles) of anhydride (AA-2), 2. 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 4.91 g of 4,4'-diamino diethylene glycol monophenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.85 g (24.5 g) of biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Millimoles), stirred at 25°C for 3 hours, and further stirred at 80°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-2). The molecular weight of PA-2 is Mw=65,500 and Mn=28,300. It is estimated that the structure of PA-2 is a structure represented by the following formula (PA-2). [Chemical formula 61]

<Synthesis of polyester polyimide resin (PA-3)> In a flask equipped with a condenser and a stirrer, while removing water, 19.4g (25 millimoles) of anhydride (AA-4), 2, 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.85 g (24.5 millimoles) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and kept at 25°C Stirred for 3 hours, and further stirred at 80°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-3). The molecular weight of PA-3 is Mw=88,500 and Mn=36,300. It is estimated that the structure of PA-3 is a structure represented by the following formula (PA-3). [Chemical formula 62]

<Synthesis of polyester polyimide resin (PA-4)> In a flask equipped with a condenser and a stirrer, while removing water, 17.9 g (25 millimoles) of anhydride (AA-5), 2, 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.85 g (24.5 millimoles) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and kept at 25°C Stirred for 3 hours, and further stirred at 80°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. This reaction liquid was added to 1.5 liters of methanol to generate a precipitate, and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-4). The molecular weight of PA-4 is Mw=88,500 and Mn=36,300. It is estimated that the structure of PA-4 is a structure represented by the following formula (PA-4). [Chemical formula 63]

<Synthesis of polyester polyimide resin (PA-9)> In a flask equipped with a condenser and a stirrer, while removing water, 15.1 g (25 millimoles) of anhydride (AA-1), 2, 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 6.87 g (24 millimoles) of bis(4-amino-3-carboxyphenyl)methane (manufactured by SEIKA CORPORATION) was added, and the mixture was stirred at 25°C for 3 hours and at 80°C for 3 hours. . Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-9). The molecular weight of PA-9 is Mw=38,200 and Mn=16,400. It is estimated that the structure of PA-9 is a structure represented by the following formula (PA-9). [Chemical formula 64]

<Synthesis of polyester polyimide resin (PA-10)> In a flask equipped with a condenser and a stirrer, while removing water, 12.44g (17.5 millimoles) of anhydride (AA-6) and anhydride ( AA-7) 3.77g (7.5 millimoles), 2,2,6,6-tetramethylpiperidine 1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03g dissolved in N-form Pyrrolidone (NMP) 80.0g. Next, 6.87 g (24 millimoles) of bis(4-amino-3-carboxyphenyl)methane (manufactured by SEIKA CORPORATION) was added, and the mixture was stirred at 25°C for 3 hours and at 80°C for 3 hours. . Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-10). The molecular weight of PA-10 is Mw=32,400 and Mn=15,200. It is presumed that the structure of PA-10 has a structure of two repeating units represented by the following formula (PA-10). In the following structural formulas, the subscripts in parentheses indicating repeating units indicate the content ratio (molar ratio) of each repeating unit. [Chemical formula 65]

<Synthesis of polyester polyimide resin (PA-11)> In a flask equipped with a condenser and a stirrer, while removing water, 15.4g (25 millimoles) of anhydride (AA-8), 2, 0.03 g of 2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 8.71 g (25 millimoles) of 4,4'-(9-fluorenylidene)diphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours. Stirring was continued for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40° C. for 1 day to obtain polyester polyimide resin (PA-11). The molecular weight of PA-11 is Mw=55,600 and Mn=22,700. It is estimated that the structure of PA-11 is a structure represented by the following formula (PA-11). [Chemical formula 66]

<Synthesis of polyester polyimide resin (PA-12)> In a flask equipped with a condenser and a stirrer, while removing water, 6.28 g (12.5 millimoles) of anhydride (AA-7) and anhydride ( AA-3) 6.53g (12.5 millimoles), 2,2,6,6-tetramethylpiperidine 1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03g dissolved in N-form Pyrrolidone (NMP) 80.0g. Next, 4,90g (24.5 millimoles) of 4,4'-diaminodiethylene glycol monophenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25°C for 3 hours. Stirring was continued for 3 hours at 80°C. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Under reduced pressure, the obtained resin was dried at 40°C for 1 day. Next, dissolve the dried resin in 70.0g of N-methylpyrrolidone (NMP), and add 2,2,6,6-tetramethylpiperidine 1-oxy radical (Tokyo Chemical Industry Co.,Ltd) . System) 0.02g, and cooled to 0 ℃. Next, 1.58 g (12.5 millimoles) of diisopropylcarbodiimide and glycidol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, it was cooled to 25°C, precipitated in 1.5 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 3,000 rpm for 30 minutes. The precipitated polyimide resin was obtained by filtration. After washing with 1 liter, the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Under reduced pressure, at 40 It was dried at ℃ for 1 day to obtain polyester polyimide resin (PA-12). The molecular weight of PA-12 is Mw=57,400 and Mn=24,800. It is inferred that the structure of PA-12 has two types of repeating units represented by the following formula (PA-12). In the formula (PA-12), * represents _{the bonding site between R 1} and the oxygen atom to be bonded. [Chemical formula 67]

<Synthesis of polyimide precursor (PI-1)> 20.0 g (64.5 millimoles) of 4,4'-oxodiphthalic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 millimoles) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 20.4 g (258 millimoles) pyridine, and 100 g diglyme were mixed and stirred at a temperature of 60°C for 18 Hours to produce a diester of 4,4'-oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl ₂ was added for 10 minutes while maintaining the temperature at -10±4°C. The viscosity increased during the addition of SOCl _2. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08g (58.7 millimoles) of 4,4'-diaminodiethylene glycol monophenyl ether dissolved in 100mL of N-methylpyrrolidone, while keeping the temperature at -5～0℃ , Added dropwise to the reaction mixture over 20 minutes. Next, after reacting the solution and the reaction mixture at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5,000 rpm. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimine precursor was dried at 45° C. for 3 days to obtain the polyimine precursor (PI-1). The weight average molecular weight of the polyimide precursor (PI-1) was 22,000. It is estimated that the structure of PI-1 is a structure represented by the following formula (PI-1). [Chemical formula 68]

<Synthesis of polyimide (A-1) for comparative example> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the 4,4'-diamino group was removed while removing water. 20.0 g (100 millimoles) of diphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200.0 g of N-methylpyrrolidone (NMP). Next, 44.4 g (100 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 50 mL of toluene, nitrogen was charged at a flow rate of 200 ml/min, and the temperature was raised to 180° C., stirred for 9 hours, and cooled to room temperature. Next, 130.0 g of N-methylpyrrolidone was added, and after diluting, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was obtained by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, in a reduced pressure state, the obtained polyimide was dried at 40° C. for 1 day to obtain the polyimide (A-1) for the comparative example. The weight average molecular weight (Mw) of A-1 is 78,200, and the number average molecular weight (Mn) is 30,500. The polyimide (A-1) for the comparative example does not contain the repeating unit represented by the formula (1-1), and does not correspond to a specific resin. It is estimated that the structure of A-1 is a structure represented by the following formula (A-1). [Chemical formula 69]

<Synthesis of polyimide (A-2) for comparative example> In a flask equipped with a condenser and a stirrer, while removing water, the anhydride (a-1) of the structure represented by the following formula (a-1) ) 11.5g (25 millimoles), 2,2,6,6-tetramethylpiperidine 1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03g dissolved in N-methylpyrrolidine Ketone (NMP) 80.0g. Next, 4.91 g of 4,4'-diamino diethylene glycol monophenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.85 g (24.5 g) of biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Millimoles), stirred at 25°C for 3 hours, and further stirred at 80°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was added to 1.5 liters of methanol to form a precipitate, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Next, in a reduced pressure state, the obtained resin was dried at 40° C. for 1 day to obtain the polyimide (A-2) for the comparative example. The molecular weight of A-2 is Mw=85,100 and Mn=36,900. The polyimide (A-2) for the comparative example does not contain the repeating unit represented by the formula (1-1), and does not correspond to a specific resin. It is estimated that the structure of A-2 is a structure represented by the following formula (A-2). [Chemical formula 70]

<Examples and Comparative Examples> In each example, the components described in the following Table 1 were mixed to obtain each curable resin composition. Moreover, in each comparative example, the components described in the following Table 1 were mixed, respectively, and each comparative composition was obtained. The obtained curable resin composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In Table 1, the numerical value in the "parts by mass" column represents the content (parts by mass) of each component. In Table 1, for example, "PA-1/PI-1" in the "Type" column and "18/14" in the "Parts by mass" column indicate that 18 parts by mass of PA-1 were used, respectively. 14 parts by mass of PI-1. In addition, in Table 1, the description of "-" indicates that the corresponding component is not contained.

[Table 1] Specific resin or comparative resin Solvent Polymerization initiator or acid generator Polymeric compound or acid crosslinking agent Polymerization inhibitor Metal adhesion improver Migration inhibitor additive Onium salt or base generator Hardening conditions Development method Developer solubility Analytic Chemical resistance species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts temperature Example 1 PA-1 32 DMSO /GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180°C Solvent A A B Example 2 PA-2 32 DMSO /GBL 60 OXE-01 1.2 SR-209 6.0 F-3 0.08 G-3 0.7 H-1 0.12 - - - - 180°C Solvent B B A Example 3 PA-3 32 DMSO /GBL 60 OXE-01 1.2 SR-209 6.0 F-1 0.08 G-1 0.7 H-1 0.12 - - - - 180°C Solvent A A A Example 4 PA-4 32 DMSO /GBL 60 OXE-01 1.2 SR-231 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180°C Solvent A A B Example 5 PA-1 /PI-1 18 /14 DMSO /GBL 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - I-1 0.5 180°C Solvent A B A Example 6 PA-1 32 NMP 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180°C Solvent A A B Example 7 PA-2 32 NMP 60 OXE-01 1.2 SR-239 6.0 F-3 0.08 G-3 0.7 H-3 0.12 - - - - 180°C Solvent B A A Example 8 PA-3 /PA-4 16 /16 NMP 60 OXE-01 1.2 ADPH 6.0 F-1 0.08 G-1 0.7 H-2 0.12 - - - - 180°C Solvent A B A Example 9 PA-9 32 DMSO /GBL 60 OXE-01 1.2 SR-209 6.0 F-2 0.08 G-1 0.7 H-1 0.12 - - - - 180°C Alkali A B B Example 10 PA-11 32 DMSO /GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-1 0.12 - - - - 180°C Solvent B B B Example 11 PA-12 32 DMSO /GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-1 0.12 - - - - 180°C Solvent B B B Example 12 PA-1 35 NMP /EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 H-2 0.12 J-1 1.08 - - 180°C Solvent A A B Example 13 PA-10 35 DMSO /GBL 60 NQD /DFY 2.5 /0.5 TMGU /ICATG 3.0 /2.0 F-2 0.05 G-1 0.7 H-1 0.12 - - - - 180°C Alkali B B A Comparative example 1 A-1 35 NMP /EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 H-2 0.12 J-1 1.08 - - 180°C Solvent C C D Comparative example 2 A-2 35 NMP /EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 H-2 0.12 J-1 1.08 - - 180°C Solvent C C D Comparative example 3 A-2 35 NMP /EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 - - J-1 1.08 - - 180°C Alkali D D C

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

[Specific resin or resin for comparison] ･PA-1～PA-11: PA-1～PA-11 synthesized in the above ･PI-1: PI-1 synthesized in the above ･A-1～A-2: A-1～A-2 synthesized above

[Solvent] ･DMSO: dimethyl sulfide ･GBL: γ-Butyrolactone ・EL: Ethyl lactate ･NMP: N-methylpyrrolidone In Table 1, the description of DMSO/GBL indicates that DMSO and GBL were mixed and used at a ratio of DMSO:GBL=20:80 (mass ratio). In Table 1, the description of NMP/El indicates that NMP and ethyl lactate were mixed and used in a ratio of NMP: ethyl lactate = 80:20 (mass ratio).

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

[Polymerizable compound or acid crosslinking agent] ･SR-209: SR-209 (manufactured by Sartomer Company, Inc) ･SR-231: SR-231 (manufactured by Sartomer Company, Inc) ･SR-239: SR-239 (manufactured by Sartomer Company, Inc) ･ADPH: Dineopentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, Ltd.) ・TMGU: 1.3.4.6-Tetra (methoxymethyl) glycoluril (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ICATG: Triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Polymerization inhibitor] ･F-1: 1,4-Benzoquinone ･F-2: 4-Methoxyphenol ･F-3: 1,4-Dihydroxybenzene ･F-4: 2-Nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Metal Adhesion Improver] ･G-1 to G-4: Compounds with the following structures. In the following structural formulae, Et represents an ethyl group. [Chemical formula 71]

(Migration inhibitor) ･H-1: 1H-tetrazole ･H-2: 1,2,4-triazole ･H-3: 5-Phenyltetrazole

[Onium salt or thermal base generator] ･I-1: Compound of the following structure [Chemical formula 72]

[additive] ･J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation> [Evaluation of the solubility of the developer] The evaluation of the solubility of the developer was carried out as follows. By the spin coating method, each curable resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied to the silicon wafer, thereby forming a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer is applied is dried on a hot plate at 100° C. for 5 minutes to obtain a uniform curable resin composition layer with a thickness of about 35 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the curable resin composition layer on the silicon wafer was exposed ^{by i-rays with an exposure energy of 500 mJ/cm 2.} The above-mentioned exposure was performed using a binary mask formed with a 1:1 line and space pattern having a width of 50 μm, a width of 70 μm, or a width of 100 μm. Regarding the curable resin composition layer after the above exposure, in the example described as "solvent" in the "Development method (developer)" column of Table 1, cyclopentanone at 30°C was used as the developer for the exposure The curable resin composition layer was developed and washed with PGMEA (propylene glycol monomethyl ether acetate). In the example described as "alkali" in the "development method (developer)" column of Table 1, for the curable resin composition layer after exposure, a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 30°C was used as The developer is developed and rinsed with ion-exchanged water. A 1:1 line and space (L/S) pattern with a width of 100μm is used for exposure, and the minimum time required to dissolve the unexposed part when the thickness of the curable resin composition layer is set to 35μm is the minimum development time , And evaluated in accordance with the following evaluation criteria. It can be said that the shorter the minimum development time, the better the solubility of the developer. The evaluation results are described in Table 1. -Evaluation Criteria- A: The above-mentioned minimum development time is within 30 seconds. B: The above-mentioned minimum development time exceeds 30 seconds and is within 60 seconds. C: The above-mentioned minimum development time exceeds 60 seconds and is within 120 seconds. D: It is not completely dissolved within 120 seconds.

〔Resolution Evaluation〕 In each example or comparative example, a silicon wafer with a curable resin composition layer was produced by the same method as the above-mentioned developer solubility evaluation, and a 1:1 line and space with a width of 70μm or a width of 100μm was used (L/S) The pattern is exposed. Except that the development time was set to a development time that was twice the minimum development time in the above-mentioned developer solubility evaluation, the development treatment and washing treatment were performed by the same method as the above-mentioned developer solubility evaluation, and then observed to show dissolution Check whether the part of the silicon wafer surface can be resolved. 27 points of the dissolved part in the pattern of the cured film after development were measured and evaluated in accordance with the following evaluation criteria. The evaluation results are described in Table 1. A: Able to analyze all 50μm L/S patterns. B: When 50μm, more than one cannot be analyzed, and all 70μm L/S patterns can be analyzed C: It is not possible to completely analyze one or more L/S patterns of 70 μm, and it is possible to analyze all L/S patterns of 100 μm. D: One or more L/S patterns of 100 μm are not completely resolved due to development residues and the like.

[Evaluation of chemical resistance] The curable resin composition or comparative composition prepared in each example and comparative example was applied to a silicon wafer by spin coating, thereby forming a curable resin composition物层。 The material layer. The silicon wafer to which the obtained curable resin composition layer is applied is dried on a hot plate at 100° C. for 5 minutes to obtain a curable resin composition layer with a uniform thickness of 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the curable resin composition layer on the silicon wafer was exposed with an exposure energy of ^{500mJ/cm 2 to expose the exposed curable resin composition layer (resin layer) to} The temperature was raised at a temperature increase rate of 10° C./min in a nitrogen environment, and the cured layer (resin layer) of the curable resin composition layer was obtained by heating for 180 minutes at the temperature described in the “curing conditions” column of Table 1. The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. Evaluation conditions: The resin layer is immersed in the chemical solution at 75°C 15 minutes, compare the film thickness before and after, calculate the dissolution rate (nm/min). The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in Table 1. It can be said that the lower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A The dissolution rate is less than 200nm/min. The dissolution rate of B is 200nm/min or more and less than 300nm/min. C The dissolution rate is 300nm/min or more and less than 400nm/min. D The dissolution rate is 400nm/min or more.

From the above results, it can be seen that the curable resin composition containing the specific resin of the present invention has excellent chemical resistance. The comparative compositions of Comparative Examples 1 to 3 do not contain a specific resin. It can be seen that the comparative compositions of Comparative Examples 1 to 3 have poor chemical resistance. <Example 101> The curable resin composition described in Example 1 was spin-coated on the surface of the copper thin layer in the resin substrate with the copper thin layer formed on the surface to have a film thickness of 20 μm. The curable resin composition coated on the resin substrate was dried at 100°C for 2 minutes, and then exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask of a square pattern (a square pattern of 100 μm in length and width, repeating counts of ten), ^{exposure was performed at a wavelength of 365 nm at an exposure amount of 400 mJ/cm 2} to create a pattern with squares remaining. After exposure, it was developed with cyclopentanone for 30 seconds and washed with PGMEA for 20 seconds to obtain a pattern. Next, the temperature was raised at a temperature increase rate of 10°C/min under a nitrogen atmosphere to reach the temperature described in the "hardening conditions" column of Example 1 in Table 1, and then heated at this temperature for 3 hours to form a re Interlayer insulating film for wiring layer. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, and as a result, it was confirmed that they were operating normally.

Claims (15)

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

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group. The curable resin composition according to claim 1, wherein the aforementioned A ¹ system contains a group including an ethylenically unsaturated bond, a cyclic ether group, or a methylol group as a polymerizable group. The curable resin composition according to claim 1 or 2, wherein It also contains a polymerization initiator and a polymerizable compound. The curable resin composition according to claim 1 or 2, wherein It also contains an acid generator and an acid crosslinking agent. The curable resin composition according to claim 1 or claim 2, wherein the aforementioned Q ¹ includes at least one selected from the group consisting of structures represented by the following formulas (A-1) to (A-5) A structure,

In formulas (A-1) to (A-5), R ^A11 to R ^A14 , R ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 each independently represent a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxyl group, cyano group, halogenated alkyl group, halogen atom or group containing a polymerizable group, L ^A31 and L ^A41 each independently represent a single bond, a carbonyl group, a sulfonyl group , A divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group or a halogenated alkylene group, * each independently represents a bonding site with another structure. The curable resin composition according to claim 1 or 2, wherein the aforementioned Q ¹ includes a polymerizable group-containing group. The curable resin composition according to claim 1 or 2, wherein Y ¹ is an n+divalent hydrocarbon group. The curable resin composition according to claim 1 or claim 2, which is used to form an interlayer insulating film for a rewiring layer. A cured film formed by curing the curable resin composition according to any one of claims 1 to 8. A laminate having two or more layers of the cured film as described in claim 9, and a metal layer between any of the foregoing cured films. A method for producing a cured film, which includes a film forming process 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 includes a process of heating the aforementioned film at 50°C to 450°C. A semiconductor device comprising the cured film according to claim 9 or the laminated body according to claim 10. A resin having a repeating unit represented by the following formula (1-1),

In formula (1-1), X ¹ and X ² each independently represent an aromatic hydrocarbon group or an aliphatic cyclic group, Y ¹ represents an n+divalent organic group, A ¹ represents a group containing a polymerizable group, and n represents 1 In the above integers, Q ¹ represents a divalent linking group. A method for manufacturing resin, which is a method for manufacturing resin as described in claim 14, which includes: A process for reacting compound A having at least two hydroxyl groups and at least one reactive group and compound B having a group capable of forming a bond with the aforementioned reactive group and a polymerizable group to obtain a diol compound; A process for reacting the aforementioned diol compound with a compound having 3 carboxyl groups or a derivative of the aforementioned compound having 3 carboxyl groups to obtain a tetravalent carboxylic acid compound having two ester bonds; The process of reacting the aforementioned tetravalent carboxylic acid compound and diamine compound to obtain a polyimide precursor; and The process of making the aforementioned polyimide precursor imidization.