TW202110950A - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor - Google Patents

Abstract

A curable resin composition including at least one resin selected from the group consisting of polyimides and polyimide precursors having a polyalkyleneoxy group and a polymerizable group, a polymerization initiator, a polymerizable compound, and a solvent; a cured film obtained by curing the curable resin composition; a laminate including the cured film; a method for producing the cured film; a semiconductor device including the cured film or the laminate; and a polyimide or a polyimide precursor.

Description

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

The present invention relates to a curable resin composition, a cured film, a laminate, a method for manufacturing a cured film, a semiconductor device, and a polyimide or polyimide precursor.

Polyimide is excellent in heat resistance and insulation, so it is suitable for various applications. The use is not particularly limited, and if a semiconductor device for actual mounting 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, and sometimes is used in the form of a curable resin composition containing a polyimide precursor. The aforementioned precursor is cyclized by heating or the like to become polyimide. These curable resin compositions can be applied to substrates and the like by known coating methods. Therefore, it can be said that, for example, the shape, size, and application position of the applied curable resin composition can be manufactured with high degree of freedom in design. The adaptability is excellent. Considering not only the high performance of polyimide, but also the excellent adaptability in manufacturing, it is increasingly expected to expand the group containing polyimine and polyimine precursors. Industrial application of a curable resin composition of at least one of the resins.

For example, Patent Document 1 describes a curable polyimide having a structure with a specific polymerizable group.

[Patent Document 1] International Publication No. 2018/237377

In a curable resin composition containing at least one resin selected from the group consisting of polyimine or polyimide precursors, it is desirable to provide a curable resin composition having excellent coating properties of the composition.

An object of one embodiment of the present invention is to provide a curable resin composition with excellent coatability, a cured film formed by curing the curable resin composition, a laminate including the cured film, and a composite of the cured film Manufacturing method and semiconductor device including the above-mentioned cured film or the above-mentioned laminate. In addition, the purpose of another aspect of the present invention is to provide a novel polyimide or polyimine precursor.

式（1-1）中，R¹ 分別獨立地表示氫原子或烷基，Z¹ 表示包含聚合性基之基團，n表示2以上的整數，m表示2以上的整數，*表示與其他結構的鍵結部位。 ＜3＞如＜2＞所述之硬化性樹脂組成物，其中上述Z¹ 作為上述聚合性基包含選自包括乙烯性不飽和基、環狀醚基及羥甲基之群組中之至少一種基團。 ＜4＞如＜2＞或＜3＞所述之硬化性樹脂組成物，其中上述樹脂作為包含以上述式（1-1）表示之結構之結構，包含以下述式（1-2）表示之結構。 [化學式2]

式（1-2）中，L¹ 表示b+2價連接基，X² 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，L² 表示單鍵或a+1價連接基，X¹ 表示以上述式（1-1）表示之結構，a表示1以上的整數，b表示1以上的整數，存在複數個X² 、L² 、X¹ 或a時，複數個X² 、L² 、X¹ 或a可以相同，亦可以不同。 ＜5＞如＜2＞至＜4＞之任一項所述之硬化性樹脂組成物，其中作為包含以上述式（1-1）表示之結構之重複單元，包含以下述式（1-3）表示之重複單元。 [化學式3]

式（1-3）中，L¹ 表示b+2價連接基，X² 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，L² 表示單鍵或a+1價連接基，X¹ 表示以上述式（1-1）表示之結構，a表示1以上的整數，b表示1以上的整數，L⁴ 表示以下述式（L4-1）或式（L4-2）表示之結構，存在複數個X² 、L² 、X¹ 或a時，複數個X² 、L² 、X¹ 或a可以相同，亦可以不同。 [化學式4]

式（L4-1）或式（L4-2）中，R¹¹⁵ 表示4價有機基，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。 ＜6＞如＜4＞或＜5＞所述之硬化性樹脂組成物，其中上述L¹ 包含選自包括以下述式（A-1）～（A-5）表示之結構之群組中之至少一種所表示之結構。 [化學式5]

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、鹵素原子或與上述式（1-2）或上述式（1-3）中的X² 的鍵結部位，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，R^A11 ～R^A14 、R^A21 ～R^A24 、R^A31 ～R^A38 、R^A41 ～R^A48 及R^A51 ～R^A58 中，b個分別為與上述式（1-2）或上述式（1-3）中的X² 的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 ＜7＞如＜1＞至＜6＞之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜8＞一種硬化膜，其係將＜1＞至＜7＞之任一項所述之硬化性樹脂組成物硬化而成。 ＜9＞一種積層體，其係具有兩層以上的＜8＞所述之硬化膜，且在硬化膜之間具有金屬層。 ＜10＞一種硬化膜的製造方法，其係包括將＜1＞至＜7＞之任一項所述之硬化性樹脂組成物適用於基材而形成膜之膜形成步驟。 ＜11＞如＜10＞所述之硬化膜的製造方法，其係包括將上述膜曝光之曝光步驟及將上述膜顯影之顯影步驟。 ＜12＞如＜10＞或＜11＞所述之硬化膜的製造方法，其係包括在50～450℃下加熱上述膜之步驟。 ＜13＞一種半導體器件，其係包含＜8＞所述之硬化膜或＜9＞所述之積層體。 ＜14＞一種聚醯亞胺或聚醯亞胺前驅物，其係包含以下述式（1-1）表示之結構。 [化學式6]

式（1-1）中，R¹ 分別獨立地表示氫原子或烷基，Z¹ 表示包含聚合性基之基團，n表示2以上的整數，m表示2以上的整數，*表示與其他結構的鍵結部位。 [發明效果]Hereinafter, examples of representative embodiments of the present invention will be described. <1> A curable resin composition containing: at least one resin having a polyalkyleneoxy group and a polymerizable group selected from the group consisting of polyimine and polyimide precursors; polymerized Starting agent; polymerizable compound; and solvent. <2> The curable resin composition according to <1>, in which the structure having the polyalkoxyl group and the polymerizable group includes a structure represented by the following formula (1-1). [Chemical formula 1]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site. <3> The curable resin composition according to <2>, wherein the Z ¹ as the polymerizable group includes at least one selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group Group. <4> The curable resin composition as described in <2> or <3>, wherein the resin includes a structure represented by the above formula (1-1) as a structure represented by the following formula (1-2) structure. [Chemical formula 2]

In formula (1-2), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, when there are multiple X ² , L ² , X ¹ or a, multiple X ² , L ² , X ¹ or a may be the same or different. <5> The curable resin composition according to any one of <2> to <4>, which includes the following formula (1-3) as a repeating unit including the structure represented by the above formula (1-1) ) Represents the repeating unit. [Chemical formula 3]

In formula (1-3), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula (L4-2) In the indicated structure, when there are a plurality of X ² , L ² , X ¹ or a, the plurality of X ² , L ² , X ¹ or a may be the same or different. [Chemical formula 4]

In formula (L4-1) or formula (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or -NH-, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom Or monovalent organic group. <6> The curable resin composition as described in <4> or <5>, wherein the L ¹ includes one selected from the group including the structures represented by the following formulas (A-1) to (A-5) At least one of the indicated structures. [Chemical formula 5]

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 the bonding site ^{with X 2 in the above formula (1-2) or the above formula (1-3), 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, R ^A11 to R ^A14 , R ^A21 to R ^{In A24} , R ^A31 to R ^A38 , R ^A41 to R ^A48, and R ^A51 to R ^A58 , b is the bonding site ^{with X 2} in the above formula (1-2) or the above formula (1-3), respectively, * Each independently indicates the bonding site with other structures. <7> The curable resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a rewiring layer. <8> A cured film obtained by curing the curable resin composition described in any one of <1> to <7>. <9> A laminate having two or more layers of the cured film described in <8>, and a metal layer between the cured films. <10> A method for producing a cured film, which includes a film forming step of applying the curable resin composition described in any one of <1> to <7> to a substrate to form a film. <11> The method for producing a cured film as described in <10>, which includes an exposure step of exposing the above-mentioned film and a development step of developing the above-mentioned film. <12> The method for producing a cured film as described in <10> or <11>, which includes the step of heating the film at 50 to 450°C. <13> A semiconductor device comprising the cured film described in <8> or the laminated body described in <9>. <14> A polyimine or polyimine precursor, which contains a structure represented by the following formula (1-1). [Chemical formula 6]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site. [Effects of the invention]

According to an embodiment of the present invention, there is provided a curable resin composition with excellent coatability, a cured film formed by curing the curable resin composition, a laminate including the cured film, and a method for manufacturing the cured film And a semiconductor device including the above-mentioned cured film or the above-mentioned laminate. Furthermore, according to another aspect of the present invention, a novel polyimide or polyimide precursor is 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 "～" means 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 "step" not only refers to an independent step, but as long as it can achieve the expected effect of the step, it also refers to a step that cannot be clearly distinguished from other steps. Regarding the label of the group (atomic group) in this specification, the label not labeling substituted and unsubstituted includes both a group (atomic group) without a substituent and a group (atomic group) with a substituent. 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 electron beams, ion beams, and other particle 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" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(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 all the components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of other components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined in accordance with gel permeation chromatography (GPC measurement) and in terms of polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and protection columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000 can be used as the tube housing. , TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the washing solution. Also, 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 layered body is described as "upper" or "lower", it is only necessary that another layer exists on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, a third layer or a third element may be further sandwiched between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. Also, unless otherwise specified, the direction in which the layers are stacked on the substrate is called "up", or when a photosensitive layer is present, the direction from the substrate to the photosensitive layer is called "up", and the opposite direction is called "under". In addition, the setting of this up-down direction is to facilitate the description of this specification. In an actual aspect, the "up" direction in this specification may also be different from the vertical up-direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may also include two or more compounds that conform to the component. In addition, unless otherwise specified, the content of each component in the composition indicates the total content of all the compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C and the pressure is 101,325Pa (1 atmosphere). In this specification, a combination of preferred aspects is a better aspect.

(Curable resin composition) The curable resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention".) contains a polyalkyleneoxy group and a polymerizable group selected from the group consisting of polyimine and polyimide precursors At least one resin in the group (hereinafter, also referred to as "specific resin"), polymerization initiator, polymerizable compound, and solvent. The curable resin composition of the present invention preferably further contains a thermal base generator or an onium salt described later. In particular, when the specific resin is a polyimide precursor, the curable resin composition of the present invention preferably further contains a thermal base generator or an onium salt described later.

The curable resin composition of the present invention is excellent in coatability. In this specification, the coating property of the composition means that the coating film formed after coating and drying has a small film thickness difference, and there are few defects such as uneven coating caused by bubbles and unevenness. The mechanism by which the above-mentioned effects can be obtained is uncertain, but it is thought that the specific resin has excellent solubility in solvents because the specific resin contains a polyalkoxyl group and a polymerizable group. It is believed that by using such a specific resin with excellent solubility, the specific resin is not easy to precipitate even when the solvent is gradually volatilized when the composition is coated and dried. Therefore, the coating film formed after coating is less likely to have a film thickness difference. And it is not easy to produce defects. In addition, it is considered that, for example, even if the curable resin composition of the present invention is used for a substrate having a step, a flat film can be easily obtained. In addition, it is considered that in the cured film obtained after curing the coating film, a rigid polyimide structure and a soft polyalkoxyl structure coexist, and therefore the strength (for example, elongation at break) of the cured film is likely to be improved.

Among them, in Patent Document 1, there is neither description nor suggestion regarding a resin containing a polyalkoxy group. In addition, the curable resin composition in Patent Document 1 has a problem of low coatability.

＜Specific resins＞ The curable resin composition of the present invention contains a specific resin. The specific resin has a polyalkoxyl group and a polymerizable group. The specific resin may have a polyalkoxyl group in the main chain, but from the viewpoint of the film strength of the cured film obtained, it is preferable to have it in the side chain of the specific resin. 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. Moreover, it is preferable that the specific resin has a side chain which has a polyalkoxyl group and a polymerizable group as a side chain.

[Polyoxyalkylene] In the present invention, the polyalkoxyl group refers to a group directly bonding two or more alkoxyl groups. The alkylene groups in the plurality of alkylene groups contained in the polyalkoxy group may be the same or different. When the polyalkoxyl group contains a plurality of different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, a block arrangement, or Arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, the carbon number including the substituent) is preferably 2 or more, more preferably 2-50, more preferably 2-30, and more preferably 2-10 Preferably, 2 to 6 are further preferred, 2 to 4 are particularly preferred, and 2 or 3 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of alkoxyl groups (the number of repetitions of polyalkoxyl groups) contained in the polyalkoxyl group is preferably from 2 to 100, more preferably from 2 to 50, and even more preferably from 2 to 30, 2-10 is particularly good, and 3-10 is the best. As a polyoxyethylene group, from the viewpoint of both solvent solubility and chemical resistance, polyvinyloxy, polypropoxy, polytrimethylene, polytetramethylene, or multiple ethyleneoxy groups are combined with Groups to which a plurality of propoxyl groups are bonded are preferred, and polyvinyloxy or polypropoxyl groups are more preferred. Among the groups in which the plural ethyleneoxy groups and the plural propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferable aspect of the repeating number of the vinyloxy group etc. in these groups is as mentioned above.

[Polymerizing group] As the polymerizable group contained in the specific resin, 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)acrylic acid group are preferred. Amino group, (meth)acryloxy group, maleimino group, vinyl phenyl group, epoxy group, oxetanyl group or methylol group are more preferable, (meth)acryloxy group Group, epoxy group or hydroxymethyl group are more preferable. As a preferable aspect of the present invention, an aspect in which a polymerizable group contained in a specific resin is directly bonded to one terminal of the above-mentioned polyalkyleneoxy group can be cited. That is, it is preferable that the specific resin has a side chain to which one end of the above-mentioned polyalkyleneoxy group is bonded to the polymerizable group.

式（1-1）中，R¹ 分別獨立地表示氫原子或烷基，Z¹ 表示包含聚合性基之基團，n表示2以上的整數，m表示2以上的整數，*表示與其他結構的鍵結部位。[Structure represented by formula (1-1)] As the structure having the above-mentioned polyalkoxyl group and the above-mentioned polymerizable group, the specific resin preferably includes a structure represented by the following formula (1-1). The specific resin preferably contains a plurality of structures represented by the following formula (1-1). When the specific resin contains a plurality of structures represented by formula (1-1), the plurality of structures represented by formula (1-1) may be the same or different. [Chemical formula 7]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site.

-R ¹ -In the formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbons, preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and a hydrogen atom Or methyl is more preferred.

式（Z-1）中，L表示單鍵或nz+1價連接基，nz表示1以上的整數，Z² 表示聚合性基，*表示與式（1-1）中的氧原子的鍵結部位。 式（Z-1）中，L為單鍵或脂肪族烴基、芳香族烴基、醚鍵（-O-）、羰基（-C（=O）-）、硫醚鍵（-O-）、磺醯基（-S（=O）₂ -）、-NR^N -、或者將該等鍵結兩個以上之基團為較佳，單鍵、脂肪族烴基或芳香族烴基為更佳。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。 作為上述脂肪族烴基，碳數1～20的烴基為較佳，碳數1～10的烴基為更佳。又，作為上述脂肪族烴基，飽和脂肪族烴基為更佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為更佳，碳數6～12的芳香族烴基為更佳，碳數6的芳香族烴基為更佳。 式（Z-1）中，nz為1～10的整數為較佳，1～4的整數為較佳，1或2為進一步較佳，1為特佳。 式（Z-1）中，nz為1，並且L為單鍵或伸烷基、伸芳基、醚鍵（-O-）、羰基（-C（=O）-）、硫醚鍵（-O-）、磺醯基（-S（=O）₂ -）、-NR^N -、或者將該等鍵結兩個以上之基團為較佳，nz為1，並且L為單鍵或碳數1～10的伸烷基、伸苯基、醚鍵（-O-）、羰基（-C（=O）-）、硫醚鍵（-O-）、磺醯基（-S（=O）₂ -）、-NR^N -、或者將該等鍵結兩個以上之基團為更佳。 式（Z-1）中，Z² 為乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基或羥甲基為更佳，（甲基）丙烯醯氧基、環氧基或羥甲基為進一步較佳。-Z ¹ -In the formula (1-1), Z ¹ represents a group containing a polymerizable group. Z ¹ as the above-mentioned polymerizable group preferably includes at least one group selected from the group consisting of ethylenically unsaturated groups, cyclic ether groups, and methylol groups, including vinyl groups, (meth)allyl groups, (Meth)acrylamido, (meth)acrylamido, maleimido, vinylphenyl, epoxy, oxetanyl or methylol is more preferred, including The (meth)acryloxy group, epoxy group or hydroxymethyl group is more preferable. In addition, Z ¹ is preferably a group represented by the following formula (Z-1). [Chemical formula 8]

In formula (Z-1), L represents a single bond or nz+1 valent linking group, nz represents an integer of 1 or more, Z ² represents a polymerizable group, and * represents a bond with the oxygen atom in formula (1-1) Location. In formula (Z-1), L is a single bond or aliphatic hydrocarbon group, aromatic hydrocarbon group, ether bond (-O-), carbonyl group (-C(=O)-), thioether bond (-O-), sulfur An acyl group (-S(=O) ₂ -), -NR ^N -, or a group bonding two or more of these groups is preferable, and a single bond, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is 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 aliphatic hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrocarbon group having 1 to 10 carbon atoms is more preferred. In addition, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. In formula (Z-1), nz is preferably an integer of 1 to 10, preferably an integer of 1 to 4, 1 or 2 is more preferred, and 1 is particularly preferred. In the formula (Z-1), nz is 1, and L is a single bond or an alkylene group, an arylene group, an ether bond (-O-), a carbonyl group (-C(=O)-), a thioether bond (- O-), sulfonyl (-S(=O) ₂ -), -NR ^N -, or a group that bonds two or more of these groups is preferred, nz is 1, and L is a single bond or carbon Number of 1-10 alkylene, phenylene, ether bond (-O-), carbonyl (-C(=O)-), thioether bond (-O-), sulfonyl (-S(=O) ) ₂ -), -NR ^N -, or it is more preferable to bond these two or more groups. In formula (Z-1), Z ² is vinyl, (meth)allyl, (meth)acrylamido, (meth)acrylamido, maleimido, ethylene A phenyl group, an epoxy group, an oxetanyl group, or a hydroxymethyl group is more preferable, and a (meth)acryloxy group, an epoxy group or a hydroxymethyl group is more preferable.

-n- In formula (1-1), n each independently is preferably an integer of 2 to 100, more preferably an integer of 2 to 50, more preferably an integer of 2 to 30, and particularly preferably an integer of 2 to 10, The integer of 3-10 is the best.

-m- In the formula (1-1), it is preferable that m is independently an integer of 2-50, an integer of 2-30 is more preferable, an integer of 2-10 is more preferable, and an integer of 2-6 is more preferable. Preferably, an integer of 2 to 4 is particularly preferred, and 2 or 3 is most preferred.

式（1-1-1）～式（1-1-3）中，n及Z¹ 的含義分別與式（1-1）中的n及Z¹ 相同，且較佳的態樣亦相同。 式（1-1-1）～式（1-1-3）中，*表示與其他結構的鍵結部位。The specific resin as the structure represented by the formula (1-1) includes a structure selected from the structure represented by the following formula (1-1-1), the structure represented by the following formula (1-1-2), and the following formula ( 1-1-3) At least one structure in the group of the indicated structures is preferable. [Chemical formula 9]

The same as in the formula (1-1-1) to (1-1-3), n and Z ¹ are the meaning of the formula (1-1) n and Z ^1, and preferred aspects are also the same. In formulas (1-1-1) to (1-1-3), * represents the bonding site with other structures.

式（1-2）中，L¹ 表示b+2價連接基，X² 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，L² 表示單鍵或a+1價連接基，X¹ 表示以上述式（1-1）表示之結構，a表示1以上的整數，b表示1以上的整數，存在複數個X² 、L² 、X¹ 或a時，複數個X² 、L² 、X¹ 或a可以相同，亦可以不同。[Structure represented by formula (1-2)] As the structure including the structure represented by the above formula (1-1), the specific resin preferably includes the structure represented by the following formula (1-2). The specific resin preferably contains a structure represented by formula (1-2) in the main chain. ^{That is, it is preferable that the structure represented by L 1} in the formula (1-2) is contained in the main chain of the specific resin. The specific resin preferably contains a plurality of structures represented by formula (1-2). When the specific resin contains a plurality of structures represented by formula (1-2), the plurality of structures represented by formula (1-2) may be the same or different. [Chemical formula 10]

In formula (1-2), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, when there are multiple X ² , L ² , X ¹ or a, multiple X ² , L ² , X ¹ or a may be the same or different.

-L ¹ -L ¹ represents a b+2 valent linking group, which is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR ^N- At least one bonded group of is preferred. 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 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 above-mentioned 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 these, from the viewpoint of solvent solubility, L 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, L ¹ preferably includes at least one structure selected from the group consisting of structures represented by any one of the following formula (A-1) to the following formula (A-5), and the following formula (A- 1) The structure represented by any one of the following formulas (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、鹵素原子或與上述式（1-2）或上述式（1-3）中的X² 的鍵結部位，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，R^A11 ～R^A14 、R^A21 ～R^A24 、R^A31 ～R^A38 、R^A41 ～R^A48 及R^A51 ～R^A58 中，b個分別為與式（1-2）或後述式（1-3）中的X² 的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。[Chemical formula 11]

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 the bonding site ^{with X 2 in the above formula (1-2) or the above formula (1-3), 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, R ^A11 to R ^A14 , R ^A21 to R ^{Among A24} , R ^A31 to R ^A38 , R ^A41 to R ^A48, and R ^A51 to R ^A58 , b is the bonding site to ^{X 2} in formula (1-2) or formula (1-3) described later, * Each independently indicates the bonding site with other structures.

From the viewpoint of chemical resistance, among these, L ¹ is preferably 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, Hydroxyl group, cyano group, halogenated alkyl group having 1 to 3 carbons or halogen atom are preferred. From the viewpoint of solvent solubility, hydrogen atom, alkyl group having 1 to 6 carbons, alkoxy group having 1 to 6 carbons Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. Further, in the R ^A11 ~ R ^A14 is one and b in the formula (1-2) or the above formula (1-3) X ² bonded portion, ^{the A13} R is bonded to X or R ² portion ^A12 and R The bonding site of ^A14 and X ^{2 is 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 the formula (A-2), ^{the meanings of R A21} to R ^{A24 are the same as those of R A11} to R ^A14 in the formula (A-1), and preferred aspects are also the same. In addition, ^{b among R A21} to R ^A24 is a bonding site to ^{X 2} in formula (1-2) or formula (1-3) described later.

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, Hydroxyl group, cyano group, halogenated alkyl group having 1 to 3 carbons or halogen atom are preferred. From the viewpoint of solvent solubility, hydrogen atom, alkyl group having 1 to 6 carbons, alkoxy group having 1 to 6 carbons Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is 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. And, X is bonded portion after the R ^A31 ~ R ^A38 is a b formula (1-2) or the following formula (1-3) ^2, R ^A31 and R ^A36 and the bonded portion of X ² is preferably . 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. The ring structure of ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, ormoline ring, etc. The ring structure removes two hydrogen atoms. good. These heterocyclic rings may further have a condensed ring with other heterocyclic rings or hydrocarbon rings. 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 have the same meanings as R A31} to R ^{A38 in} formula (A-3), and preferred aspects are also the same. And, X is bonded portion after the R ^A41 ~ R ^A48 is a b formula (1-2) or the following formula (1-3) ^2, R ^A41 and R ^A48 and the bonded portion of X ² is preferably . In formula (A-4), L ^{A41 has the same meaning as L A31} in formula (A-3), and preferred aspects are also the same.

In the formula (A-5), ^{the meanings of R A51} to R ^{A58 are the same as those of R A11} to R ^A14 in the 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 in the resin independently.

-X ² -In the formula (1-2), X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and an ester bond or an ether bond is preferred. In addition, X ² may be determined in consideration of the synthesis method and the like. When X ² is an ester bond, the carbon atom of the ester bond may be bonded to L ¹ or the oxygen atom may be bonded to L ¹ . When X ² is a urethane bond, the oxygen atom of the urethane bond is preferably ^{bonded to L 1.} When X ² is an amide bond, the carbon atom of the amide bond is preferably ^{bonded to L 1.}

-L ² -In the formula (1-2), L ² represents a single bond or a + 1 valent linking group, a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group,- NR ^N -, or a group that bonds two or more of these groups is preferable, and a single bond, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is 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 aliphatic hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrocarbon group having 1 to 10 carbon atoms is more preferred. In addition, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.

-X ¹ -In the formula (1-2), X ¹ represents the structure represented by the above formula (1-1), and a preferable aspect is as described in the description of the formula (1-1).

-a- In the formula (1-2), a represents an integer of 1 or more, and an integer of 1 to 10 is preferred, 1 to 4 is more preferred, 1 or 2 is more preferred, and 1 is particularly preferred.

-b- In the formula (1-2), b represents an integer of 1 or more, and an integer of 1 to 10 is preferred, 1 to 4 is more preferred, 1 or 2 is more preferred, and 1 is particularly preferred.

式（1-3）中，L¹ 表示b+2價連接基，X² 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，L² 表示單鍵或a+1價連接基，X¹ 表示以上述式（1-1）表示之結構，a表示1以上的整數，b表示1以上的整數，L⁴ 表示以下述式（L4-1）或式（L4-2）表示之結構，存在複數個X² 、L² 、X¹ 或a時，複數個X² 、L² 、X¹ 或a可以相同，亦可以不同。 [化學式13]

式（L4-1）或式（L4-2）中，R¹¹⁵ 表示4價有機基，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。[Repeating unit represented by formula (1-3)] As a repeating unit including a structure represented by formula (1-1), the specific resin preferably includes a repeating unit represented by the following formula (1-3). In addition, the specific resin preferably has a repeating unit represented by formula (1-3) in the main chain. [Chemical formula 12]

In formula (1-3), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linking group, X ¹ represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula (L4-2) In the indicated structure, when there are a plurality of X ² , L ² , X ¹ or a, the plurality of X ² , L ² , X ¹ or a may be the same or different. [Chemical formula 13]

In formula (L4-1) or formula (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or -NH-, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom Or monovalent organic group.

-L ¹ , X ² , L ² , X ¹ , a and b- In formula (1-3), L ¹ , X ² , L ² , X ¹ , a and b have the same meaning as formula (1-2) L ¹ , X ² , L ² , X ¹ , a and b are the same, and preferred aspects are also the same.

-L ⁴ -<<Formula (L4-1)>> In the formula (L4-1), R ¹¹⁵ is preferably a tetravalent organic group containing an aromatic ring, which is represented by the following formula (5) or formula (6) The group is more preferable.

[Chemical formula 14]

R ¹¹² is a divalent linking group, a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may 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, a single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-,- The group in C(=O)-, -S- and -S(=O) ₂ -is more preferably selected from the group including -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.} * Each independently indicates the bonding site with other structures.

^{The tetravalent organic group represented by R 115} in the formula (L4-1) specifically includes a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride. 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 15]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same meaning as in formula (L4-1) of the R ^115.

As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic 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-di Carboxyphenyl) 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 alkyl derivatives with 1 to 6 carbon atoms and carbon numbers At least one of 1 to 6 alkoxy derivatives.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below can also be mentioned.

[Chemical formula 16]

<<Formula (L4-2)>> In the formula (L4-2), A ¹ and A ² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred. In the formula (L4-2), 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 both of them contain a polymerizable group. Better. Examples of the polymerizable group in R ¹¹³ or R ¹¹⁴ include the same groups as the polymerizable group ^{in Z 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 17]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and 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). In addition, (poly)alkoxyl group means an alkoxyl group or a polyalkoxyl group. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are more good. 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 (L4-2) has one, two or three (preferably one) acid groups, aliphatic groups, Aromatic groups and aralkyl groups, etc. 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 a hydrogen atom, and it is more preferable that a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group are used.

From the viewpoint of solubility in an organic solvent, 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 sulphur ring, a pentene ring, and an indene ring. Ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, terphenylene ring, etc.) or substituted or Unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, pyrrole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrimidine ring) , Scalp ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, quinoline ring, naphthyridine ring, quinoline Ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, chromene ring, Kouyamaguchi ring, phenanthrene ring, phenanthrene ring Or brown 𠯤 ring).

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the repeating unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is actually 50% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, the aliphatic group having a silicone structure can be copolymerized with a specific resin. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

In formula (L4-2), R ¹¹⁵ is the same meaning as in formula (L4-1) R ^115, and preferably also of the same aspect.

-Resin Type-In the formula (1-3), when L ⁴ is a structure represented by a group represented by the formula (L4-1), the specific resin is preferably polyimide. In formula (1-3), when L ⁴ is a structure represented by a group represented by formula (L4-2), it is preferable that the specific resin is a polyimide precursor.

-content- When the specific resin contains the repeating unit represented by the formula (1-3), the content of the repeating unit represented by the formula (1-3) relative to the total mass of the specific resin is preferably 0.1-80 mass%, 0.5-70 mass % Is more preferable, and 1 to 60% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-3), or may include two or more types.

式（1-1B）中，R^B1 分別獨立地表示氫原子或烷基，nB表示2以上的整數，mB表示2以上的整數，*分別獨立地表示與其他結構的鍵結部位。[Structure represented by formula (1-1B)] The specific resin may include a structure represented by the following formula (1-1B) and have a polymerizable group in another part of the specific resin. The specific resin may have a structure represented by the following formula (1-1B) in the main chain, or may have it in a side chain. From the viewpoint of film strength, it is preferable to have it in the main chain. In addition, from the viewpoint of coatability, it is preferable to have it in the side chain. [Chemical formula 18]

In formula (1-1B), R ^B1 each independently represents a hydrogen atom or an alkyl group, nB represents an integer of 2 or more, mB represents an integer of 2 or more, and * each independently represents a bonding site with another structure.

-R ^B1 -In the formula (1-1B), R ^{B1 is} each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom Or methyl is more preferred.

-nB- In formula (1-1B), nB each independently is preferably an integer of 2-100, more preferably an integer of 2-50, more preferably an integer of 2-30, and particularly preferably an integer of 2-10. The integer of 3-10 is the best.

-mB- In the formula (1-1B), it is preferable that m is independently an integer of 2-50, an integer of 2-30 is more preferable, an integer of 2-10 is more preferable, and an integer of 2-6 is more preferable. Preferably, an integer of 2 to 4 is particularly preferred, and 2 or 3 is most preferred.

式（1-1B-1）～式（1-1B-3）中，nB的含義分別與式（1-1B）中的nB相同，且較佳的態樣亦相同。 式（1-1B-1）～式（1-1B-3）中，*分別獨立地表示與其他結構的鍵結部位。As the structure represented by the formula (1-1B), the specific resin includes a structure selected from the structure represented by the following formula (1-1B-1), the structure represented by the following formula (1-1B-2), and the structure represented by the following formula ( 1-1B-3) At least one structure in the group of structures indicated is preferable. [Chemical formula 19]

In formulas (1-1B-1) to (1-1B-3), nB has the same meaning as nB in formula (1-1B), and preferred aspects are also the same. In formulas (1-1B-1) to (1-1B-3), * each independently represents a bonding site with other structures.

式（1-2B）中，L^B1 及L^B2 分別獨立地表示單鍵或2價連接基，L^X 表示以上述式（1-1B）表示之結構。 式（1-2C）中，L^B3 表示單鍵或2價連接基，L^X 表示以上述式（1-1B）表示之結構，R^B2 表示氫原子或表示不具有聚合性基的取代基。[Formula (1-2B) or Formula (1-2C)] The specific resin as a structure including formula (1-1B) includes a structure represented by the following formula (1-2B) or a structure represented by the following formula (1-2C) The structure is better. When the specific resin includes a structure represented by the following formula (1-2B), the specific resin preferably includes a structure represented by the following formula (1-2B) in the main chain. When the specific resin contains the structure represented by the following formula (1-2C), the specific resin preferably contains the structure represented by the following formula (1-2C) at the end of the main chain or on the side chain, and more preferably contains the structure on the side chain . The specific resin preferably contains a plurality of structures represented by formula (1-2B) or structures represented by formula (1-2C). When the specific resin contains multiple structures represented by formula (1-2B) or structures represented by formula (1-2C), multiple structures represented by formula (1-2B) or structures represented by formula (1-2C) The structure can be the same or different. [Chemical formula 20]

In the formula (1-2B), L ^B1 and L ^B2 each independently represent a single bond or a divalent linking group, and L ^X represents a structure represented by the above formula (1-1B). In the formula (1-2C), L ^B3 represents a single bond or a divalent linking group, L ^X represents a structure represented by the above formula (1-1B), and R ^B2 represents a hydrogen atom or a substituent that does not have a polymerizable group.

In the formula (1-2B), L ^B1 and L ^B2 are each independently a single bond or an alkylene group, an aryl group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or the like It is preferable to bond two or more groups, a single bond, an alkylene group or an arylene group is more preferable, and a single bond or an alkylene group is 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 above-mentioned alkylene group, an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, and an ethylene group or a propylene group is more preferable. In the formula (1-2B), L ^X represents the structure represented by the above formula (1-1B), and a preferable aspect is as described in the description of the above formula (1-1B).

In formula (1-2C), L ^{B3 has the same meaning as L B1} or L ^B2 in the above formula (1-2B), and preferred aspects are also the same. In the formula (1-2C), L ^X represents the structure represented by the above formula (1-1B), and a preferable aspect is as described in the description of the above formula (1-1B). In the formula (1-2C), R ^B2 only needs to be a hydrogen atom or a known substituent such as an alkyl group, an aryl group, and a halogen atom. A hydrogen atom, an alkyl group or an aryl group is preferred, and a hydrogen atom or an alkyl group is more preferred. Preferably, the alkyl group is further preferred. As the above-mentioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aryl group, an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 6 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

式（1-3B）中，L^B1 及L^B2 分別獨立地表示單鍵或2價連接基，L^X 表示以上述式（1-1B）表示之結構，L^B4 表示以上述式（1-3）中的式（L4-1）或式（L4-2）表示之結構。[Repeating unit represented by formula (1-3B)] When the specific resin includes a structure represented by formula (1-2B), it is preferable that the specific resin includes a repeating unit represented by the following formula (1-3B). [Chemical formula 21]

In the formula (1-3B), L ^B1 and L ^B2 each independently represent a single bond or a divalent linking group, L ^X represents the structure represented by the above formula (1-1B), and L ^B4 represents the above formula (1-3 The structure represented by the formula (L4-1) or formula (L4-2) in ).

In the formula (1-3B), the meaning of L ^B1, L ^B2 and L ^X, respectively of formula (1-2B) L ^B1, L ^B2 and L ^X identical, and preferred aspects are also the same. In the formula (1-3B), L ^{B4 has the same meaning as L 4} in the above formula (1-3), and preferred aspects are also the same.

- the type of resin - when the formula (1-3B), L ^B4 is a group represented by the formula (L4-1) represented by the structure, the specific resin is a polyimide is preferred. When the formula (1-3B), L ^B4 is a group represented by the formula (L4-2) represented by the structure, the specific resin is a polyimide precursor is preferred.

-content- When the specific resin contains the repeating unit represented by the formula (1-3B), the content of the repeating unit represented by the formula (1-3B) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 70 mass% % Is more preferable, and 20 to 60% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-3B), or may include two or more types.

式（1-3C）中，L^B5 表示nB2+2價連接基，X^B2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，X^B1 表示以上述式（1-2C）表示之結構，nB2表示1以上的整數，存在複數個X^B1 或X^B2 時，複數個X^B1 或X^B2 可以相同，亦可以不同。[Structure represented by formula (1-3C)] When the specific resin includes the structure represented by formula (1-2C), the specific resin as the structure including the structure represented by formula (1-2C) includes the following formula (1 -3C) The structure indicated is better. The specific resin preferably contains a structure represented by formula (1-3C) in the main chain. That is, in the formula (1-3C) L ^B5 is preferably represented by the structures contained in the main chain of the specific resin. The specific resin preferably contains a plurality of structures represented by formula (1-3C). When the specific resin contains a plurality of structures represented by formula (1-3C), the plurality of structures represented by formula (1-3C) may be the same or different. [Chemical formula 22]

In formula (1-3C), L ^B5 represents nB2+divalent linking group, X ^B2 represents ester bond, urethane bond, urea bond, amide bond or ether bond, X ^B1 represents the formula (1-2C ) Represents the structure, nB2 represents an integer of 1 or more. When there are multiple X ^B1 or X ^B2 , the multiple X ^B1 or X ^B2 may be the same or different.

In the formula (1-3C), L ^{B5 has the same meaning as L 1} in the above formula (1-2), and preferred aspects are also the same. When the formula L ^B5 includes any of the structures represented by the formulas (A-1) to (A-5), "R ^A11 to R ^A14 , R in the description of the formulas (A-1) to (A-5) ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48, and R ^A51 to R ^A58 are the bonding sites ^{of X 2} in formula (1-2) or formula (1-3) described later, respectively , "may be replaced by" the ^{R A11 ~ R A14, R A21} ~ R A24, R A31 ~ R A38, R A41 ~ R A48 and R ^A51 ~ R ^A58 are in a nB2 formula (2-1) X The bonding part of ^B2,". In the formula (1-3C), X ^{B2 has the same meaning as X 2} in the above formula (1-2), and preferred aspects are also the same. In the formula (1-3C), X ^B1 represents the structure represented by the above formula (1-2C), and a preferable aspect is as described in the description of the above formula (1-2C). In the formula (1-3C), nB2 has the same meaning as b in the above formula (1-2), and preferred aspects are also the same.

式（1-4C）中，L^B5 表示nB2+2價連接基，X^B2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，X^B1 表示以上述式（1-2C）表示之結構，nB2表示1以上的整數，L^B4 表示以上述式（1-3）中的式（L4-1）或式（L4-2）表示之結構，存在複數個X^B1 或X^B2 時，複數個X^B1 或X^B2 可以相同，亦可以不同。[Repeating unit represented by formula (1-4C)] When the specific resin contains the structure represented by the formula (1-2C) or the structure represented by the formula (1-3C), the specific resin contains the following formula (1-4C) The repeating unit shown is preferred. [Chemical formula 23]

In formula (1-4C), L ^B5 represents nB2+divalent linking group, X ^B2 represents ester bond, urethane bond, urea bond, amide bond or ether bond, X ^B1 represents the formula (1-2C ) Represents the structure, nB2 represents an integer of 1 or more, L ^B4 represents the structure represented by the formula (L4-1) or the formula (L4-2) in the above formula (1-3), there are plural X ^B1 or X ^B2 At the time, a plurality of X ^B1 or X ^B2 may be the same or different.

In the formula ^{(1-4C), L B5, X} B2, X B1 and nB2 meaning as in the formula ^{(1-3C) L B5, X B2} , X ^B1 and nB2 are the same, and preferably also the aspect of the same. In formula (1-4C), L ^{B4 has the same meaning as L 4} in the above formula (1-3), and preferred aspects are also the same.

- the type of resin - when the formula (1-4C), L ^B4 is a group represented by the formula (L4-1) represented by the structure, the specific resin is a polyimide is preferred. When the formula (1-4C), L ^B4 is a group represented by the formula (L4-2) represented by the structure, the specific resin is a polyimide precursor is preferred.

-content- When the specific resin contains the repeating unit represented by the formula (1-4C), the content of the repeating unit represented by the formula (1-4C) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 80 mass% % Is more preferable, and 20 to 75% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-4C), or may include two or more types.

式（2-1）中，L²¹ 表示b2+2價連接基，X²² 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵，X²¹ 表示包含聚合性基之基團，X²¹ 及X²² 為不包含聚伸烷氧基的基團，b2表示1以上的整數，L⁴ 表示以上述式（1-3）中的式（L4-1）或式（L4-2）表示之結構，存在複數個X²² 或X²¹ 時，複數個X²² 或X²¹ 可以相同，亦可以不同。[Repeating unit represented by formula (2-1)] The specific resin may further include a repeating unit represented by the following formula (2-1). In addition, when the specific resin includes a structure represented by formula (1-2B) or formula (1-2C), the specific resin includes polymerization in a structure other than the structure represented by formula (1-2B) or formula (1-2C) Sex-based. When the specific resin is a polyimide, it is preferable that the specific resin further includes a repeating unit represented by the following formula (2-1) and L ²¹ is a formula (L4-1) as a repeating unit having a polymerizable group. Specific resin is polyimide precursor, L ^B4 specific resin of the repeating unit represented by the formula (1-3B) or the repeating unit represented by the formula (1-4C) L ^B4 is a polymerizable group, Or it is preferable to further include the repeating unit represented by the following formula (2-1) and L ²¹ is a formula (L4-2). When the repeating unit represented by the repeating unit represented by the formula (1-3B) of formula L ^B4 or (1-4C) L ^B4 is a polymerizable group, L ^B4 above formula (L4-2) and formula It is preferable that at least one ^{of R 113} and R ¹¹⁴ in (L4-2) contains a polymerizable group. [Chemical formula 24]

In formula (2-1), L ²¹ represents a b2+divalent linking group, X ²² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and X ²¹ represents a group containing a polymerizable group , X ²¹ and X ²² are groups that do not contain a polyalkyleneoxy group, b2 represents an integer of 1 or more, and L ⁴ represents the formula (L4-1) or the formula (L4-2) in the above formula (1-3) ) Indicates the structure. When there are multiple X ²² or X ²¹ , the multiple X ²² or X ²¹ may be the same or different.

In formula (2-1), ^{the meanings of L 21} , X ²² , b2 and L ⁴ are the same as those of L ¹ , X ² , b and L ⁴ in the above formula (1-3), and preferred aspects are also the same. When formula L ²¹ includes any one of the structures represented by formulas (A-1) to (A-5), "R ^A11 to R ^A14 , R in the description of formulas (A-1) to (A-5) ^A21 to R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48, and R ^A51 to R ^A58 are the bonding sites ^{of X 2} in formula (1-2) or formula (1-3) described later, respectively ," can be replaced with "R ^A11 ～R ^A14 , ^RA21 ～ ^RA24 , ^RA31 ～ ^RA38 , ^RA41 ～ ^RA48 and ^RA51 ～R ^A58 where b2 is the same as X in formula (2-1) The bonding part of ^22,". In the formula (2-1), X ²¹ represents a group containing a polymerizable group, and the group represented by the above formula (Z-1) is preferred.

-Resin Type-In the formula (2-1), when L ⁴ is a structure represented by a group represented by the formula (L4-1), the specific resin is preferably a polyimide. In formula (2-1), when L ⁴ is a structure represented by a group represented by formula (L4-2), it is preferable that the specific resin is a polyimide precursor.

-content- When the specific resin contains the repeating unit represented by the formula (2-1), the content of the repeating unit represented by the formula (1-4C) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 80 mass% % Is more preferable, and 20 to 75% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (2-1), or may include two or more types.

式（4）中，R¹³¹ 表示2價有機基，R¹³² 表示4價有機基。[Other repeating units] -Repeating units represented by the formula (4)- The specific resin may further include a repeating unit represented by the following formula (4). When the specific resin contains a repeating unit represented by the following formula (4), the specific resin is preferably polyimide. When the specific resin includes a repeating unit represented by the following formula (4), the specific resin preferably includes a repeating unit represented by the following formula (4) in the main chain. [Chemical formula 25]

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 R 111} in the formula (1) described later can be exemplified, and the preferable range is also the same. As ^{the tetravalent organic group represented by R 132 , the same group as R 115} in the above formula (L4-1) can be exemplified, and the preferred range is also the same.

^{When R 1 in} the structure represented by formula (1-1) in the specific resin is a substituent that does not include a polymerizable group, ^{at least one of R 131} and R ¹³² may include a polymerizable group, or may be in the polyamide The terminal of the imine has a structure containing a polymerizable group.

When the specific resin contains the repeating unit represented by formula (4) (for example, when the specific resin is polyimide), the specific resin contains 1 to 80% by mass relative to the total mass of the specific resin expressed by formula (4) The repeating unit is preferable, and it is more preferable to contain 10 to 70% by mass, and it is still more preferable to contain 20 to 60% by mass. In addition, when the specific resin is polyimide, it can also be set to a state where the specific resin does not substantially contain the repeating unit represented by the formula (4). In this aspect, the repeating unit represented by the formula (4) is The content is preferably 5% by mass or less with respect to the total mass of the specific resin, and more preferably 1% by mass or less. In addition, when the specific resin is polyimide, the repeating unit represented by formula (1-3), the repeating unit represented by formula (1-3B), and the repeating unit represented by formula (1-4C) contained in the specific resin The total content of the repeating unit, the repeating unit represented by formula (2-1), and the repeating unit represented by formula (4) (in the above repeating unit, there may be repeating units not included) relative to the total mass of the specific resin 50 to 100% by mass is preferable, 60 to 99% by mass is more preferable, and 70 to 95% by mass is still more preferable.

A¹ 及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。-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 is preferably a polyimide precursor. When the specific resin contains a repeating unit represented by the following formula (1), the specific resin preferably has a repeating unit represented by the following formula (1) in the main chain. [Chemical formula 26]

A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.

(1) In the ^{formula, A 1, A 2, R} 113, R ^114, and the meanings of R ¹¹⁵ each independently have the above formula ^{(L4-2) A 1, A 2} , R 113, R ¹¹⁴ and R ¹¹⁵ identical , And the preferred aspect is also the same. In formula (1), R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or a combination of two or more of these groups, with a carbon number of 2 -20 linear aliphatic groups, branched aliphatic groups with 3-20 carbons, cyclic aliphatic groups with 3-20 carbons, aromatic groups with 6-20 carbons, or a combination of these Two or more groups are preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred.

^{Preferably, R 111} in the formula (1) is derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, the diamine contains a linear aliphatic group having 2 to 20 carbons, a branched or cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination of these Diamines with two or more groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

[Chemical formula 27]

In the formula, A is a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may 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, a single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- and -S(=O) ₂ -is more preferably selected from the group including -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.}

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane 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'-dimethyl Cyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4 , 4'-diaminodiphenyl sulfide or 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl 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-hydroxyphenyl)sulfonate, Bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-( 4-aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy) phenyl] ash, bis[4-(2-aminophenoxy) phenyl] ash, 1 ,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Supplement, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3 ,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diamine Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraamino Diphenyl ether, 1,4-diaminoanthraquinone, 1 ,5-Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) stilbene, 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, ethyl Guanidine, 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-aminophenyl)ethyl Alkyl, diaminobenzaniline, diaminobenzoic acid, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl) ) Hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-amine Phenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy) )Phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4 -Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4' -Bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4' -Bis(4-amino-2-trifluoromethylphenoxy)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'-hexafluorotolidine And at least one diamine in 4,4'-diaminotetrabiphenyl.

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

[Chemical formula 28]

[Chemical formula 29]

Moreover, as a preferable example, the diamine which has at least two alkylene glycol units in the main chain can also be mentioned. Preferably, a diamine containing two or more of ethylene glycol chains and propylene glycol chains or both in total is preferable in one molecule, and a diamine that does not contain an aromatic ring is more preferable. 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 trade 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 30]

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

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ in the formula (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 represents a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- Or these groups can be combined with two or more groups. The meaning of the preferable range of L ⁰ is the same as the above-mentioned A.

From the viewpoint of i-ray transmittance, R ¹¹¹ in the formula (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 31]

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 group 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). 6) The fluorinated alkyl group and so on.

[Chemical formula 32]

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.

Examples of the diamine compound imparting the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

When the specific resin contains the repeating unit represented by the formula (1) (for example, when the specific resin is a polyimide precursor), the specific resin contains 1 to 90% by mass relative to the total mass of the specific resin in accordance with formula (1) The indicated repeating unit is preferable, and it is more preferable to contain 10 to 80% by mass, and it is more preferable to contain 20 to 70% by mass. In addition, when the specific resin is a polyimide precursor, it can also be set to a state in which the specific resin does not substantially contain the repeating unit represented by formula (1). In this aspect, the repeating unit represented by formula (1) The content of the unit relative to the total mass of the specific resin is preferably 5% by mass or less, and more preferably 1% by mass or less. In addition, when the specific resin is a polyimide precursor, the repeating unit represented by the formula (1-3), the repeating unit represented by the formula (1-3B), and the repeating unit represented by the formula (1-4C) contained in the specific resin The total content of the repeating unit represented, the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (1) (in the above repeating units, there may be repeating units not included) relative to the total content of the specific resin The mass is preferably from 50 to 100% by mass, more preferably from 60 to 99% by mass, and even more preferably from 70 to 95% by mass.

[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 with respect 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 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) of the specific resin is preferably 800-250,000, more preferably 2,000-50,000, and still more preferably 4,000-25,000. The molecular weight dispersion of the specific resin is preferably 1.5 to 3.5, and more preferably 2 to 3. In this specification, the degree of molecular weight dispersion means 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 in the solvent development described below, 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 aforementioned acid group means a group neutralized by a base having a pH of 12 or higher (for example, sodium hydroxide). Moreover, it is preferable that the said acid group is a group with 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.

[Preferred Aspects of Specific Resin] The specific resin is at least one resin selected from the group consisting of polyimine and polyimide precursors. In the following description, the repeating unit represented by the formula (1-3) and L ⁴ is the formula (L4-1) is referred to as repeating unit PI-1. It will be represented by the formula (1-3B) and L ^B4 repeating units of formula (L4-1) of the repeating units called PI-2. It will be represented by the formula (1-4C) and repeating units of the formula L ^B4 (L4-1) of the repeating units called PI-3. The repeating unit represented by formula (2-1) and L ⁴ of formula (L4-1) is referred to as repeating unit PI-4. The repeating unit represented by formula (1-3) and L ⁴ of formula (L4-2) is referred to as repeating unit PIP-1. The repeating unit represented by formula (1-3B) and L ^B4 of formula (L4-2) is referred to as repeating unit PIP-2. The repeating unit represented by formula (1-4C) and L ^B4 of formula (L4-2) is referred to as repeating unit PIP-3. The repeating unit represented by formula (2-1) and L ⁴ of formula (L4-2) is referred to as repeating unit PIP-4.

-Polyimide- When the specific resin is a polyimide, the specific resin is preferably the polyimide described in any one of the following PI1 to the following PI3. PI1: Polyimine containing repeating unit PI-1 PI2: Polyimide containing repeating unit PI-2 and repeating unit PI-4 PI3: Polyimide containing repeating unit PI-3 and repeating unit PI-4 The polyimide described in PI1 may further include the repeating unit PIP-1. The polyimide described in PI2 may further include at least one selected from the group consisting of the repeating unit PIP-2 and the repeating unit PIP-4. The polyimide described in PI3 may further include at least one selected from the group consisting of the repeating unit PIP-3 and the repeating unit PIP-4. The polyimide described in PI1 may further include a repeating unit PI-4. The polyimide described in PI1 may further include a repeating unit PI-4. The polyimide described in the above PI1 to PI3 may further include other repeating units such as the repeating unit represented by formula (4). When the polyimide described in PI1 to PI3 includes a repeating unit represented by formula (4), it may further include a repeating unit represented by formula (1).

In addition, when the specific resin is polyimide, the ring closure rate of the specific resin is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. When the specific resin is polyimide, the ring closure rate of the specific resin is a value represented by the following formula CR (PI). Type CR (PI): Ring-closure rate of specific resin (%)=(mole amount of imidine ring in specific resin)/(mole amount of iminium ring in specific resin + ring-closure in specific resin to form imines The molar amount of the structure of the ring)×100 For example, when the specific resin is a resin including the repeating unit PI-1, the repeating unit PIP-1, the repeating unit represented by formula (4), and the repeating unit represented by formula (1), the ring closure rate is determined by the following formula CR (PI) Value represented by 1. Formula CR (PI) 1: The ring-closure rate of the specific resin (%)=(mole amount of repeating unit PI-1+mole amount of repeating unit represented by formula (4))/(mole amount of repeating unit PI-1+repeat unit PIP- The molar amount of 1 + the molar amount of the repeating unit represented by formula (4) + the molar amount of the repeating unit represented by formula (1))

-Polyimine precursor- When the specific resin is a polyimide precursor, the specific resin is preferably the polyimide described in any one of PIP1 to PIP5 below. PIP1: including a repeating unit of the polyimide precursor PIP1 PIP2: comprising repeating units PIP2, formula (1-3B) L ^B4 of formula (L4-2), the formula (L4-2) in At least one of R ¹¹³ and R ¹¹⁴ includes a polyimide precursor PIP3 of a polymerizable group: a polyimide precursor PIP4 that includes a repeating unit PIP-2 and a repeating unit PIP-4: includes a repeating unit PIP-3 , L ^B4 in formula (1-3B) is formula (L4-2), ^{and at least one of R 113} and R ¹¹⁴ in formula (L4-2) contains a polyimide precursor PIP5 of a polymerizable group: Polyimide precursor containing repeating unit PIP-3 and repeating unit PIP-4

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

[resolve resolution] The specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the below-mentioned examples.

When the specific resin is the polyimide described in PI1, the specific resin is synthesized by sequentially performing, for example, the steps described in (1) to (2) below. (1) Reacting a diamine having a functional group such as a carboxyl group, a hydroxyl group, and an amino group with a dicarboxylic acid or a dicarboxylic acid derivative. After the reaction, thermal imidization or chemical imidization (for example, by using The role of catalyst to promote the cyclization reaction) and other methods to form the imine ring to obtain the step of polyimine (2) Making a compound having a group capable of bonding to the above functional group (for example, a hydroxyl group, a carboxyl group that can be halogenated, an isocyanate group, etc.), a polyalkyleneoxy group, and a polymerizable group (for example, polyalkylene two The step of reacting alcohol monomethacrylate, etc.) with the above functional group in the polyimide obtained in (1) above As a compound having a group capable of bonding to the above functional group, a polyalkyleneoxy group, and a polymerizable group, commercially available products can be used. Examples of commercially available products include BLEMMER PE-90, PE-200, and PE-350 , PP-1000, PP-500, PP-800, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800 (all manufactured by NOF CORPORATION), etc.

When the specific resin is the polyimide described in PI2, the specific resin is synthesized by sequentially performing, for example, the steps described in (3) to (4) below. (3) Diamines with polyalkyleneoxy groups (for example, bis(2-(3-aminopropoxy)ethyl)ether, etc.), diamines with functional groups such as carboxyl, hydroxyl, and amino groups, and The reaction of dicarboxylic acid or dicarboxylic acid derivative, followed by thermal imidization, chemical imidization (for example, by using a catalyst to promote the cyclization reaction) to form an imide ring , The steps to obtain polyimide (4) A compound having a group capable of bonding to the above functional group (for example, a hydroxyl group, a halogenated carboxyl group, an isocyanate group, etc.) and a polymerizable group (for example, methacrylic acid chloride, etc.) are combined with the above (1 Steps of reacting the above functional groups in the polyimine obtained in)

When the specific resin is the polyimide described in PI3, the specific resin is synthesized by sequentially performing, for example, the steps described in (5) to (6) below. (5) Reacting diamines with functional groups such as carboxyl groups, hydroxyl groups, and amino groups with dicarboxylic acids or dicarboxylic acid derivatives, followed by thermal imidization and chemical imidization (for example, by using The role of catalyst to promote the cyclization reaction) and other methods to form the imine ring to obtain the step of polyimine (6) Making a compound having a group capable of bonding to the above-mentioned functional group (for example, a hydroxyl group, a carboxyl group that can be halogenated, an isocyanate group, etc.) and a polyalkyleneoxy compound (for example, a polyalkylene glycol monoalkyl group) Ether, etc.), and compounds having a group capable of bonding to the above-mentioned functional group (for example, a hydroxyl group, a halogenated carboxyl group, an isocyanate group, etc.) and a polymerizable group (for example, hydroxyethyl methacrylate, etc.) The step of reacting with the above functional group in the polyimide obtained in (1) above

As a synthesis method when the specific resin is a polyimide precursor, for example, the reaction of a diamine and a dicarboxylic acid derivative in which at least one of a polyalkyleneoxy group and a polymerizable group is introduced into a part of the carboxylic acid can be mentioned.的方法。 The method. As the above-mentioned diamine, a diamine having a polyalkoxy group can also be used.

＜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 polyimide or polyimide precursors that are different from the specific resin. When the specific resin is polyimide, the other resin is preferably polyimide. When the specific resin is a polyimide precursor, the other resin is preferably a polyimide precursor.

[Polyimide (other resin)] From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide, which is another resin, has the repeating unit represented by the above formula (4). In the 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 may also include other types of repeating units.

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

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

Polyimine is obtained, for example, by heating or cyclizing a polyimide precursor which is another resin described later.

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

In the polyimide precursor, the repeating unit represented by the formula (1) may be one type or two or more types. In addition, the structural isomer of the repeating unit represented by formula (1) may also be included. In addition to the repeating unit of the above formula (1), the polyimide precursor may also include other types of repeating units.

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and 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 is preferably 1.5-3.5, more preferably 2-3.

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

In the production method of 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 the polyimide precursor, it is preferable to include a step of separating out solids. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent capable of dissolving the polyimide precursor, such as tetrahydrofuran, so that a solid can be precipitated.

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 More preferably, 2% by mass or more is 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 relative to the total solid content of the curable resin composition is preferably 80% by mass or less, 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.

The curable resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more types are contained, the total amount is preferably in the above-mentioned range.

＜Polymerization initiator＞ The curable resin composition of the present invention contains a polymerization 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 interacts with a light-excited sensitizer and generates 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 details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, 0138 to 0151 of International Publication No. 2015/199219, and this content is 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 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (brand names: all manufactured by BASF SE) can be used.

As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (brand names: all manufactured by BASF SE), which are commercially available products, 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 (brand 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. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred.

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 33]

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, Japanese Patent Publication 2012-014052 The photo-radical polymerization initiator described in 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 34]

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, 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 group or biphenyl group substituted with at least one of an alkyl group having 2 to 18 and an alkyl group having 1 to 4 carbons, R ^I01 is a group represented by formula (II), or the same group ^{as R I00} Group, 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 35]

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 the photopolymerization initiator is contained, 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 kind or two or more kinds. When two or more kinds of photopolymerization initiators are contained, it is preferable that the total of them is in the above-mentioned range.

[Thermal polymerization initiator] The curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator, and in particular, may contain 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 a thermal radical polymerization initiator, when the specific resin is a polyimide precursor, the precursor can be cyclized, and the specific resin and polymerizable compound can be polymerized, so higher heat resistance can be achieved化.

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 contained, 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 quality%. 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 of them is preferably in the above-mentioned range.

＜Polymerizable compound＞ [Free radical polymerizable compound] The curable resin composition of the present invention 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 possessed by 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 fifteen or less, more preferably ten or less, and even more preferably eight or less.

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. Moreover, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or more 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, hexylene glycol ) 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 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., dineopentylerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentyl erythritol 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 three different 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 radically polymerizable compound may also be a radically 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. 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 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 a 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 pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid Allyl compounds such as allyl esters, 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.

[Polymerizable compounds other than the above-mentioned radically polymerizable compounds] The curable resin composition of the present invention can further contain a polymerizable compound other than the above-mentioned radical polymerizable compound. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having methylol, alkoxymethyl, or oxymethyl; epoxy compounds; oxetane compounds; Compound.

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

（式中，t表示1～20的整數，R¹⁰⁴ 表示碳數1～200的t價有機基，R¹⁰⁵ 表示以-OR¹⁰⁶ 或-OCO-R¹⁰⁷ 表示之基團，R¹⁰⁶ 表示氫原子或碳數1～10的有機基，R¹⁰⁷ 表示碳數1～10的有機基。） [化學式37]

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基，R⁴⁰⁵ 表示以-OR⁴⁰⁶ 或-OCO-R⁴⁰⁷ 表示之基團，R⁴⁰⁶ 表示氫原子或碳數1～10的有機基，R⁴⁰⁷ 表示碳數1～10的有機基。） [化學式38]

（式中，u表示3～8的整數，R⁵⁰⁴ 表示碳數1～200的u價有機基，R⁵⁰⁵ 表示以-OR⁵⁰⁶ 或-OCO-R⁵⁰⁷ 表示之基團，R⁵⁰⁶ 表示氫原子或碳數1～10的有機基，R⁵⁰⁷ 表示碳數1～10的有機基。）[Chemical formula 36]

(In the formula, t represents an integer from 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , and R ¹⁰⁶ represents a hydrogen atom or An organic group having ^{1 to 10 carbon atoms, R 107} represents an organic group having 1 to 10 carbon atoms.) [Chemical formula 37]

(In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbons, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbons. , R ⁴⁰⁷ represents an organic group having 1 to 10 carbons.) [Chemical formula 38]

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol) Wait.

Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

-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, the inclusion of an epoxy compound indicates that the low-temperature curing and warpage of the curable resin composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the coefficient of elasticity is further reduced, and 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 bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether Polyalkylene glycol type epoxy resins such as ethers; epoxy-containing polysiloxanes such as polymethyl(glycidoxypropyl)siloxanes, etc., but are not limited to these. 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 (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name above, manufactured by ADEKA CORPORATION), etc. Among them, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

-Oxetane compounds (compounds with oxetanyl groups)- 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 compounds (compounds with polybenzo azole groups)- Since the benzoxa compound is derived from the cross-linking reaction of the ring-opening addition reaction, it does not produce outgassing during hardening, and further reduces heat shrinkage and suppresses warpage, so it is preferable.

As a preferable example of the benzoglyph compound, there can be mentioned Ba-type benzoglyph, Bm-type benzoglyph (the above are trade names, manufactured by Shikoku Chemicals Corporation), and the benzoglyphthylene resin of polyhydroxystyrene. Finished product, novolac-type dihydrobenzo 㗁𠯤 compound. These can be used alone or in combination of two or more.

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

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

＜Solvent＞ The curable resin composition of the present invention contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate , Butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3- Alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate Ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2- Ethyl methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate , Propylpyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, etc. are preferred.

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, propylene glycol monopropyl ether acetate, etc. The better.

As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones, for example.

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferred.

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 Etc. as the better ones.

Regarding the solvent, from the viewpoint of improvement of coating surface properties, etc., a form in which two or more types 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 , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of 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 the amount is 5 to 75% by mass. More preferably, it is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 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 kinds of solvents are contained, the total of them is preferably in the above-mentioned range.

＜Hot acid generator＞ The curable resin composition of the present invention preferably contains a thermal acid generator. The thermal acid generator is capable of generating acid by heating, and promotes selected from compounds having methylol, alkoxymethyl, or acyloxymethyl, epoxy compounds, oxetane compounds, and benzox compounds The effect of the crosslinking reaction of at least one compound or the methylol contained in the specific resin. Furthermore, when the curable resin composition of the present invention contains a thermal acid generator, it is preferable that the specific resin contains a methylol group as a polymerizable group.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. 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 to measure 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.

＜Onium salt＞ The curable resin composition of the present invention preferably contains an onium salt. In particular, when the specific resin is a polyimide precursor, the curable resin composition preferably contains 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, an 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 may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or an intermolecular salt in which cation molecules and anion molecules are ionically bonded as separate molecules. Intermolecular salts For 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, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and phosphonium cations is more good.

The onium salt used in the present invention may also be a thermal base generator. The thermal base generator means 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 means a salt of an ammonium cation and an 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 39]

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 40]

In Formula (Y1-1) and (Y1-2), R ¹⁰¹ represents a n-valent organic group, with the same meaning as R in formula (101) R ¹ is ^1, 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. For the reason that the stability and thermal decomposition of the salt can be balanced, 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 41]

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

In this embodiment, the electron withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Yufu Tono, 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 whose 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 42]

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 43]

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 ( An anion having a pKaH) of 2.5 or less is preferred, and an anion having a pKaH) of 1.8 or less is 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 44]

[Imine salt] In the present invention, the imine salt means a salt of an imine cation and an 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 45]

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 的含義與式（102）中的R⁵ 相同，R⁷ 的含義與式（102）中的R⁷ 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 of the following formulas (Y1-3) to (Y1-5). [Chemical formula 46]

In Formula (Y1-3) ~ (Y1-5), R 101 represents a n-valent organic group, with the same meaning as R in formula (102) ⁵ R ^5, and R in the meaning of formula (102) ⁷ R ⁷ 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 47]

[Salt] In the present invention, a sulfonium salt means 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 48]

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 these, as the substituent, it is preferable to have an alkyl group or an alkoxy group, and it is more preferable to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbons or one having 1 to 10 carbons Alkoxy 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, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt 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 49]

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, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt 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 are mentioned. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 50]

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 may be 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 in the above-mentioned range.

<Thermal base generator> The curable resin composition of the present invention may contain a thermal base generator. In particular, when the specific resin is a polyimide precursor, the curable resin composition preferably contains a thermal alkali generator. The thermal base generator may be a compound conforming to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt. 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 51]

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 ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferable.

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 also have substituents within the range in which the effects of the present invention are exhibited. 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 52]

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 group (the carbon number is 2-12 is preferable, and 2-12 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), 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 53]

^{The meanings of Rb 11} and Rb ^{12 are the} same as Rb ¹¹ and Rb ¹² in formula (B1-1). 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 1-24, 1-12 is more preferable, and 3-8 is more preferable), alkenyl (the carbon number is preferably 2-12, more preferably 2-12, 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55]

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 54]

[Chemical formula 55]

[Chemical formula 56]

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 in the above-mentioned range.

＜Migration inhibitor＞ The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing 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 57]

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.

There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, it is preferable that the total of them is in 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, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butyl phenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Phenol, 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-tertiarybutyl)phenylmethane, 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 58]

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the curable resin composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. Preferably, 0.05 to 2.5% by mass is more preferable.

There may be only one type of polymerization inhibitor, or two or more types. When there are two or more polymerization inhibitors, it is preferable that the sum total is the above-mentioned range.

＜Metal adhesion improver＞ The curable resin composition of the present invention preferably contains a metal adhesive improving agent for improving the adhesiveness with metal materials used for electrodes, wiring, and the like. As the metal adhesion improver, a silane coupling agent and the like can be mentioned.

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.

[Chemical formula 59]

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.

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 be higher than the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes better, and by setting it to be less than the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, it is preferable that the sum total is 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, as a sensitizer, a sensitizing dye can also be used. Regarding the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and the 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, for example, in 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 SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or they can be deprotonated to generate free radicals after being oxidized. 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. There may be only one type of chain transfer agent, or two or more types. When there are two or more chain transfer agents, the total of them is preferably in 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 60]

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% %. There may be only one type of surfactant, or two or more types. When there are two or more surfactants, it is preferable that the sum total is the above-mentioned range.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition due to 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. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total of them is preferably in the above-mentioned 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 of these metals is preferably in 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 suppressing 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 be in the above-mentioned ranges.

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 filter pore size is 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 step of the filter, multiple filters may 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 after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. 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. In addition, it can also be used for the formation of an insulating film of a semiconductor device, the formation of a stress buffer film, and the like.

(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminated body, 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 the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more, for example. 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 above-mentioned first cured film and the curable resin composition of the present invention for forming the above-mentioned 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, and an interlayer insulating film), or a case where a pattern is formed by etching an insulating film for actual mounting purposes as described above, etc. can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Yamin/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 in the present invention can also be used in the production 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, and the like.

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 step of applying the curable resin composition of the present invention to a substrate to form a film. Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming step, and further includes an exposure step of exposing the above-mentioned film and a development step of developing the above-mentioned film (performing a development process on the above-mentioned film). Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming step (and the above-mentioned development step as necessary), and further includes a heating step of heating the above-mentioned film at 50 to 450°C. Specifically, it is also preferable to include the following steps (a) to (d). (A) Film formation step of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (B) Exposure step of exposing the film after the film formation step (C) The developing step of developing the above-mentioned exposed film (D) Heating step of heating the developed film at 50～450℃ By heating in the above heating step, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the above-mentioned hot alkali generator is decomposed, and sufficient hardenability 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, and after forming a cured film, the step (a) or the steps (a) to (c) or the steps (a) to (d) are performed again. step. In particular, it is preferable to perform the above-mentioned steps multiple 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 steps (a) to (d), and it is possible to perform at least (a), preferably (a) to (c) or (a) to multiple times as described above. In the step (d), a laminated body of a cured film is obtained. <Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film formation step (layer formation step) of applying a curable resin composition 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 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 the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the 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 a spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. 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 step＞ The production method of the present invention may also include a step of drying in order to remove the solvent after the film formation step (layer formation step) after the film (curable resin composition layer) is formed. 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.

<Exposure Step> The manufacturing method of the present invention may also include an exposure step 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, 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.

<Development step> The manufacturing method of the present invention may also include a development step of developing the exposed film (curable resin composition layer). By performing development, 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. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, there is no particular limitation on its use. 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. It is more preferable that the developer in alkaline development is 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. There may be only one kind of basic compound, or two or more kinds. When there are two or more basic compounds, the total of them is preferably in the above-mentioned range.

In solvent development, it is more preferable that the developer contains more than 90% 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 aromatic hydrocarbons For example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sulphurite, dimethyl sulphite can be preferably cited.

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

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 also be further rinsed after the treatment with the developer. In the case of solvent development, it is better to use an organic solvent different from the developer for rinsing. 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 step＞ The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450°C (heating step). It is preferable to include a heating step after the film formation step (layer formation step), the drying step, and the development step. The curable resin composition of the present invention contains a polymerizable compound other than the specific resin, but in this step, the unreacted polymerizable compound other than the specific resin can be cured and the unreacted polymerizable group in the specific resin can be cured. 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, in the heating step, for example, the thermal alkali generator is decomposed, thereby generating alkali and causing the polyimide precursor to proceed. Cyclization reaction. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is more 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 start of heating refers to the temperature at the start of the step 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 the treatment before raising the temperature from 25°C to 180°C at 3°C/min, and keeping it at 180°C for 60 minutes, heating it from 180°C to 200°C at 2°C/min, and keeping it at 200°C for 120 minutes. step. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferable to perform treatment while irradiating with ultraviolet rays. Through these pretreatment steps, the characteristics of the film can be improved. The pretreatment step may be carried out in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be a two-stage or more step. For example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

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

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

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

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.

＜Layering Steps＞ Preferably, the manufacturing method of the present invention further includes a layering step.

The lamination step includes on the surface of the cured film (resin layer) or metal layer, and again in sequence (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step A series of steps. Among them, it may be an aspect in which only (a) the film forming step is repeated. In addition, the heating step (d) may be performed collectively at the end or in the middle of the build-up. That is, it is also possible to adopt a configuration in which the steps (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, the (e) metal layer forming step may be included after the (c) development step. 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. It goes without saying that the above-mentioned drying step and heating step can be further included in the layering step as appropriate.

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

The above-mentioned layering step is preferably performed 2 to 5 times, and more preferably 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 enumerated to repeat (a) a film formation step, (b) an exposure step, (c) a development step, (e) a metal layer formation step, (d) a heating step, or repeat sequentially ( a) Film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step in the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be 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，R¹ 分別獨立地表示氫原子或烷基，Z¹ 表示包含聚合性基之基團，n表示2以上的整數，m表示2以上的整數，*表示與其他結構的鍵結部位。(Polyimine or polyimine precursor) The polyimine or polyimine precursor of the present invention preferably includes a structure represented by the following formula (1-1). [Chemical formula 61]

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site.

The meaning of the above formula (1-1) is the same as the formula (1-1) in the specific resin, and preferred aspects are also the same. The polyimine or polyimine precursor of the present invention has the same meaning as the polyimine or polyimine precursor in the above specific resin except that the above formula (1-1) is used as a necessary condition, and is more The good looks are the same.

＜Use＞ The polyimide or polyimine precursor of the present invention is preferably used as the resin contained in the curable resin composition. In addition, there are no particular restrictions on compositions using conventional polyimide or polyimide precursors such as compositions for interlayer insulating films, and the polyimide or polyimide precursor of the present invention can be used To replace part or all of the conventional polyimide or polyimide precursor. It is considered that the composition containing the polyimide or polyimine precursor of the present invention has excellent coating properties. Therefore, the polyimide or polyimine precursor of the present invention is used, for example, in a composition for forming an insulating film. It is preferably used in a composition used in applications where a coating film is formed by coating. [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 example 1: Synthesis of polyimide (PI-1)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the 3 15.21 g (100 millimoles) of 5-diaminobenzoic acid was dissolved in 130.0 g of N-methylpyrrolidone (NMP). Next, 31.02 g (100 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 28.4 g (100 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, 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 removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-1. The weight average molecular weight (Mw) of PI-1 is 29,500, and the number average molecular weight (Mn) is 13,500. It is estimated that the structure of PI-1 is a structure represented by the following formula (PI-1). Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=91 and q=9. [Chemical formula 62]

上述（PI-2）中，C₃ H₆ 的記載中，隨機包含1-甲基伸乙基（下述（P1））和2-甲基伸乙基（下述（P2））。下述式（P1）及式（P2）中，*¹ 與式（PI-2）中的羰基側的結構鍵結，*² 與式（PI-7）中的丙烯醯氧基側的結構鍵結。 [化學式64]

<Synthesis example 2: Synthesis of polyimide (PI-2)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 31.02 g (100 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 33.6 g (80 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (90 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, 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 removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-2. The weight average molecular weight (Mw) of PI-2 is 25,100, and the number average molecular weight (Mn) is 12,100. It is estimated that the structure of PI-2 is a structure represented by the following formula (PI-2). Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=85 and q=15. [Chemical formula 63]

In the above (PI-2), in _{the description of C 3} H ₆ , 1-methylethylene ((P1) below) and 2-methylethylene ((P2) below) are randomly included. In the following formulas (P1) and (P2), * ¹ is bonded to the structure on the carbonyl side of the formula (PI-2), and * ² is bonded to the structure on the propyleneoxy group side of the formula (PI-7) Knot. [Chemical formula 64]

<Synthesis Example 3: Synthesis of Polyimide (PI-3)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the bis(4-amino- 14.3 g (50 millimoles) of 3-carboxyphenyl)methane was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Next, 9.31 g (30 millimoles) of oxydiphthalic dianhydride and 8.88 g (20 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while being charged with nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 5 hours. After cooling the above reaction liquid to 25°C, 14.2 g (50 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 6.3 g (50 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or lower for 5 hours, and the temperature was raised to room temperature. Next, 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 removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-3. The weight average molecular weight (Mw) of PI-3 is 31,000, and the number average molecular weight (Mn) is 13,900. It is estimated that the structure of PI-3 is a structure represented by the following formula (PI-3). In the formula (PI-3), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 65]

<Synthesis Example 4: Synthesis of Polyimide (PI-4)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 15.51 g (50 millimoles) of oxydiphthalic dianhydride and 22.1 g (50 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 7.80 g (60 millimoles) of 2-hydroxyethyl methacrylate, 13.6 g (40 millimoles) of hexaethylene glycol monomethyl ether, N,N'-di 0.61 g (5 millimoles) of methylaminopyridine, 0.06 g of p-methoxyphenol, and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, 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 removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-4. The weight average molecular weight (Mw) of PI-4 is 28,300, and the number average molecular weight (Mn) is 13,000. It is estimated that the structure of PI-4 is a structure represented by the following formula (PI-4). In the formula (PI-4), * represents _{the bonding site where R 1} is bonded to the oxygen atom. Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=50 and q=50. [Chemical formula 66]

上述（PI-5）中，C₃ H₆ 的記載中，隨機包含1-甲基伸乙基（上述（P1））和2-甲基伸乙基（上述（P2））。式（P1）及式（P2）中，*¹ 與式（PI-5）中的R₁ 中的丙烯酸酯基側的結構鍵結，*² 與式（PI-5）中的R₁ 中的*側的結構鍵結。<Synthesis example 5: Synthesis of polyimide (PI-5)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 15.5 g (50 millimoles) of oxydiphthalic dianhydride and 13.3 g (30 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 21.3 g (50 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 2.22 g (30 millimoles) of 1-hydroxy-2,3-propylene oxide, and N , N'-dimethylaminopyridine 0.61g (5 millimoles), p-methoxyphenol 0.06g, and N-methylpyrrolidone 130.0g were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, 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 removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-5. The weight average molecular weight (Mw) of PI-5 is 33,300, and the number average molecular weight (Mn) is 15,000. It is estimated that the structure of PI-5 is a structure represented by the following formula (PI-5). In the formula (PI-5), * represents _{the bonding site where R 1} is bonded to the oxygen atom. [Chemical formula 67]

In the above (PI-5), _{the description of C 3} H ₆ randomly includes 1-methylethylene (the above (P1)) and 2-methylethylene (the above (P2)). In formula (P1) and formula (P2), * ¹ is bonded to the structure on the side of the acrylate group in R ₁ in formula (PI-5) ^{, and * 2} _{is bonded to the structure in R 1} in formula (PI-5) *Structural bonding on the side.

<Synthesis Example 6: Synthesis of Polyimide (PI-6)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the bis(2-(3- Aminopropoxy) ethyl) ether 6.91g (30 millimoles), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 25.6g (70 millimoles) dissolved in N -Methylpyrrolidone (NMP) 100.0g. Next, 310.2 g (100 millimoles) of oxydiphthalic dianhydride and 13.3 g (30 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. 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 and stirred for 5 hours, and the reaction liquid was cooled to 25°C. 12.1 g (120 millimoles) of triethylamine, 0.06 g of p-methoxyphenol, and 80.0 g of N-methylpyrrolidone were added to dissolve, and the mixture was cooled to 0°C. Then, 10.4 g (100 millimoles) of methacrylic acid chloride was added dropwise for 1 hour, and the mixture was stirred at 25°C or lower for 4 hours. Next, 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 removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-6. The weight average molecular weight (Mw) of PI-6 is 29,900, and the number average molecular weight (Mn) is 14,300. It is estimated that the structure of PI-6 is a structure represented by the following formula (PI-6). In the formula (PI-6), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 68]

<Synthesis Example 7: Synthesis of Polyimide (PI-7)> Except for replacing 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane used in the synthesis of PI-6 PI-7 was synthesized by the same method as PI-6 except for the same molar amount of 4,6-dihydroxy-1,3-phenylenediamine. The weight average molecular weight (Mw) of PI-7 is 27,400, and the number average molecular weight (Mn) is 13,300. It is estimated that the structure of PI-7 is a structure represented by the following formula (PI-7). In the formula (PI-7), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 69]

＜合成例9：聚醯亞胺（PI-9）的合成＞ 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中，一邊去除水分，一邊將3,5-二胺苯甲酸4.56g（30毫莫耳）及9,9-雙（4-胺基-3-甲基苯基）茀7.53g（20毫莫耳）溶解於N-甲基吡咯啶酮（NMP）80.0g中。接著，添加氧二鄰苯二甲酸二酐15.51g（50毫莫耳），並在40℃的溫度下攪拌了2小時。接著，添加30mL甲苯之後，一邊充入200ml/min的流量的氮，一邊使溫度升溫至180℃，並攪拌了5小時。將上述反應液冷卻至25℃之後，添加BLEMMER PE-200（NOF CORPORATION製）14.2g（50毫莫耳）、N,N’-二甲基胺基吡啶0.61g（5毫莫耳）、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解，並冷卻為0℃。接著，添加二異丙基碳二亞胺6.3g（50毫莫耳），並在10℃以下攪拌5小時，並使其升溫至室溫。接著，將其冷卻為25℃，使其在1.5升水/甲醇=75/25（體積比）中沉澱，並以2,000rpm的速度攪拌了30分鐘。過濾去除所析出之聚醯亞胺樹脂，用1升水進行沖洗之後，將過濾物混合於1.5升甲醇中，再次攪拌30分鐘並再次進行了過濾。在減壓狀態下，將所獲得之聚醯亞胺在40℃下乾燥1天，而獲得了PI-9。PI-9的重量平均分子量（Mw）為31,600，數量平均分子量（Mn）為11,500。 推測PI-9的結構為以下述式（PI-9）表示之結構。式（PI-9）中，*表示R₁ 與氧原子鍵結之鍵結部位。 又，方括號的附註表示各重複單元的含有比（莫耳比），m=3、q=2。 [化學式71]

<Synthesis Example 8: Synthesis of Polyimide (PI-8)> Except for replacing 2-hydroxyethyl methacrylate and hexaethylene glycol monomethyl ether used in the synthesis of PI-4, dimethylglycerol was used PI-8 was synthesized in the same manner as PI-4 except for the base acrylate (manufactured by NOF CORPORATION) 30 (millimolar) and BLEMMER PE-200 (manufactured by NOF CORPORATION) (70 millimolar). The weight average molecular weight (Mw) of PI-8 is 25,900, and the number average molecular weight (Mn) is 12,900. It is estimated that the structure of PI-8 is a structure represented by the following formula (PI-8). In the formula (PI-8), * represents _{the bonding site where R 1} is bonded to the oxygen atom. [Chemical formula 70]

<Synthesis Example 9: Synthesis of Polyimide (PI-9)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 3,5-diaminobenzene was removed while removing water. Formic acid 4.56g (30 millimoles) and 9,9-bis(4-amino-3-methylphenyl) 7.53g (20 millimoles) dissolved in N-methylpyrrolidone (NMP) 80.0 g中. Next, 15.51 g (50 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 30 mL of toluene, the temperature was increased to 180° C. while being charged with nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 5 hours. After cooling the above reaction liquid to 25°C, 14.2 g (50 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 6.3 g (50 millimoles) of diisopropylcarbodiimide was 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 2,000 rpm for 30 minutes. The precipitated polyimide resin was removed by filtration, and after rinsing with 1 liter of water, the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Under reduced pressure, the obtained polyimine was dried at 40°C for 1 day to obtain PI-9. The weight average molecular weight (Mw) of PI-9 is 31,600, and the number average molecular weight (Mn) is 11,500. It is estimated that the structure of PI-9 is a structure represented by the following formula (PI-9). In the formula (PI-9), * represents _{the bonding site where R 1} is bonded to the oxygen atom. Note that the square brackets indicate the content ratio (molar ratio) of each repeating unit, m=3 and q=2. [Chemical formula 71]

上述（PA-1）中，C₃ H₆ 的記載中，隨機包含1-甲基伸乙基（上述（P1））和2-甲基伸乙基（上述（P2））。式（P1）及式（P2）中，*¹ 與式（PA-1）中的R中的丙烯醯氧基側的結構鍵結，*² 與式（PA-1）中的R中的*側的結構鍵結。<Synthesis Example 10: Synthesis of Polyimide Precursor (PA-1)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, the oxodiphthalene was removed while removing water. 20.0 g (64.5 millimoles) of dicarboxylic dianhydride was suspended in 140 mL of diglyme. Continuously add 10.1g (77 millimoles) of 2-hydroxyethyl methacrylate, 12.6g (39 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 0.05g of hydroquinone and 10.7g (135 millimoles) of pyridine ) And stirred for 18 hours at 60°C. Next, after cooling the mixture to -20°C, 16.1 g (135.5 millimoles) of sulfite chloride was added dropwise for 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, when 11.7 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent solution, the dripping was completed for 1 hour. During the addition of the above diamine, the viscosity increases. Next, 5.6 g (17.5 millimoles) of methane and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, under a reduced pressure state, the obtained polyimide precursor resin was dried at 45°C for 1 day. Regarding the molecular weight of the polyimide precursor PA-1, Mw=25,100 and Mn=13,200. It is estimated that the structure of PA-1 is a structure represented by the following formula (PA-1). In the formula (PA-1), * represents the bonding site where R and the oxygen atom are bonded. [Chemical formula 72]

In the above (PA-1), _{the description of C 3} H ₆ randomly includes 1-methylethylene (the above (P1)) and 2-methylethylene (the above (P2)). In formula (P1) and formula (P2), * ¹ is bonded to the structure on the propyleneoxy group side of R in formula (PA-1), and * ² is bonded to * in R in formula (PA-1) Structural bonding on the side.

<Synthesis Example 11: 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' -31.0g (100 millimoles) of diaminodiphenyl ether is dissolved in 180.0g of N-methylpyrrolidone (NMP). Next, 4,4 '- (hexafluoro isopropylidene) diphthalic acid dianhydride, 44.4g (100 mmol), and stirred for 2 hours at a temperature of 40 ℃. 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 6 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 2000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under a reduced pressure state, the obtained polyimide was dried at 40°C for 1 day to obtain A-1. The weight average molecular weight (Mw) of A-1 is 30,100, and the number average molecular weight (Mn) is 14,500. It is estimated that the structure of A-1 is a structure represented by the following formula (A-1). The polyimide precursor (A-1) for the comparative example does not contain a polyalkyleneoxy group and a polymerizable group, and is not a specific resin. [Chemical formula 73]

<Synthesis Example 12: Synthesis of Polyimide (A-2) for Comparative Example> Put 155.1g of 4,4'-oxodiphthalic dianhydride (ODPA) into the separable flask, and add 134.0g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400ml. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction is over, it is allowed to stand to cool to room temperature, and then to stand for 16 hours.

Next, under ice-cooling conditions, while stirring a solution of 206.3 g of dicyclohexanecarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone, it was added to the reaction mixture for 40 minutes. Next, while stirring a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone, the suspension was added for 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirring was carried out for 1 hour. After that, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate composed of crude polymer was produced. The produced crude polymer was recovered by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was recovered by filtration and then vacuum-dried to obtain a powdery polyimide precursor (A- for Comparative Example). 2). The weight average molecular weight (Mw) of the polyimide precursor (A-2) for the comparative example was measured, and the result was 20,000.

<Synthesis Example 13: Synthesis of Polyimide Precursor (A-3) for Comparative Example> In Synthesis Example 12, in place of 155.1 g of 4,4'-oxodiphthalic dianhydride, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used in order to synthesize The reaction was carried out in the same manner as the method described in Example 18, thereby obtaining the polyimide precursor (A-3) for the comparative example. The weight average molecular weight (Mw) of the polyimide precursor (A-3) for the comparative example was measured, and the result was 22,000.

The polyimide precursors (A-2) and (A-3) used in the comparative example do not contain polyalkoxy groups and are not specific resins.

<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, "PI-1/PI-2" in the "Type" column, and "16/16" in the "Parts by mass" column indicate that 16 parts by mass of PI-1 were used, and 16 Parts of PI-2 by mass. 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 Polymeric compound Polymerization inhibitor Metal adhesion improver Migration inhibitor Thermal alkali generator additive Hardening conditions Coatability Membrane strength 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 PI-1 32 DMSO/GBL 60 OXE-01 1.2 SR-209 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180°C A A 2 PI-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 A B 3 PI-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 A B 4 PI-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 B B 5 PI-5 32 DMSO/GBL 60 OXE-02 1.2 SR-209 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180°C A B 6 PI-6 32 DMSO/GBL 60 OXE-01 1.2 SR-231 6.0 F-3 0.08 G-2 0.7 H-1 0.12 - - - - 180°C B A 7 PI-7 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 B A 8 PI-8 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 A B 9 PI-9 32 DMSO/GBL 60 OXE-01 1.2 A-DPH 6.0 F-2 0.08 G-3 0.7 H-1 0.12 - - - - 180°C B B 10 PI-1 32 NMP 60 OXE-02 1.2 SR-209 6.0 F-2 0.08 G-2 0.7 H-1 012 - - - - 180°C A A 11 PI-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 A B 12 PI-1 /PI-2 16 /16 NMP 60 OXE-01 1.2 SR-268 6.0 F-1 0.08 G-1 0.7 H-2 0.12 - - - - 180°C A A 13 PA-1 32 DMSO/GBL 60 OXE-01 1.2 SR-209 6.0 F-2 0.08 G-2 0.7 H-2 0.12 I-1 0.5 - - 200°C A B 14 PA-1 33 NMP 60 OXE-01 1.2 SR-268 6.0 F-1 0.08 G-1 0.7 H-2 0.12 I-1 0.5 - - 180°C A B 15 PA-1 34.8 NMP/Ethyl Lactate 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 - - - - J-1 1.4 200°C A A Comparative example 1 A-1 32 DMSO/GBL 60 OXE-01 1.2 SR-209 6.0 F-2 0.08 G-2 0.7 H-2 0.12 - - - - 180°C C C 2 A-2 /A-3 17.4 /17.4 NMP/Ethyl Lactate 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2 /G-4 0.2 /0.2 - - - - J-1 1.4 200°C D C

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

[Specific resin or resin for comparison] ･PI-1～PI-8: PI-1～PI-8 synthesized above ･PA-1: PA-1 synthesized in the above ･A-1～A-3: A-1～A-3 synthesized above

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

[Polymerization initiator] ･OXE-01: IRGACURE OXE 01 (made by BASF SE) ･OXE-02: IRGACURE OXE 02 (made by BASF SE)

[Polymerizable compound] ･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) ･SR-268: SR-268 (manufactured by Sartomer Company, Inc) ･A-DPH: Dineopentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL 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 74]

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

[Thermal base generator] ･I-1: Compound of the following structure [Chemical formula 75]

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

＜Evaluation＞ In each of the Examples and Comparative Examples, the prepared curable resin composition or the comparative composition was used to evaluate the coatability and film strength (elongation at break). The evaluation method in each evaluation is specifically described below.

[Coatability] A total of 10 silicon stepped substrates with 100 μm in length, 20 μm in width, and 5 μm in depth were formed on one side of a silicon substrate with a diameter of 4 inches. Fig. 1 is a schematic view of the formed stepped substrate. In FIG. 1, a total of 10 steps 2 in 5 columns and 2 rows are formed on the surface of a silicon substrate 1. In FIG. 1, the step 2 is a step having a depth of 5 μm with respect to the surface of the portion of the silicon substrate 1 where the step is not formed. In addition, in each of the 10 levels, the depths of the levels are basically the same. In Fig. 1, A represents the longitudinal length of the step 2, which is 100 μm. In Fig. 1, B represents the lateral length of the level difference 2, which is 20 μm. In Figure 1, the interval of the 5 steps arranged in the horizontal direction are all 1mm. In Figure 1, the distance between the two levels arranged in the longitudinal direction is 2mm.

Each curable resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied to the stepped substrate shown in FIG. 1 by a spin coating method, thereby forming a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer with a uniform thickness of about 15 μm was obtained on the silicon wafer. The surface of the cured resin composition layer after drying was observed by AFM (Atomic Force Microscope), and the height difference of the film measured by the following formula FL was calculated. Formula FL: film height difference = (maximum height of the curable resin composition layer)-(minimum height of the curable resin composition layer) In addition, the optical microscope defect inspection device KLA2360 (manufactured by Applied Materials, Inc.) and Review SEM Vision G3 (manufactured by Applied Materials, Inc.) observed the surface of the cured resin composition layer after drying, and calculated the number of defects ^{per 1 cm 2.} Using the difference in film thickness and the number of defects as indicators, the applicability was evaluated in accordance with the following evaluation criteria. The evaluation results are described in the "Applicability" column of Table 1. The smaller the height difference of the film and the smaller the number of defects, the better the coating properties of the composition. -Evaluation Criteria- A: The height difference of the film is less than 0.3 μm, and the number of defects is less than 5/cm ² . B: The height difference of the film is less than 0.3 μm, and the number of defects is 5/cm ² or more and less than 10/cm ² . C: The height difference of the film is 0.3 μm or more and less than 0.5 μm, and the number of defects is less than 10/cm ² . D: At least one condition is satisfied out of the difference in film height of 0.5 μm or more and the number of defects of 10/cm ^{2 or more.}

[Film strength (elongation at break)] 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 was applied was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer with a uniform thickness of about 15 μm was obtained on the silicon wafer. The obtained curable resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature described in the "curing conditions" column of Table 1, it was heated at that temperature 3 hours. The cured resin layer (cured film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured film was peeled from the silicon wafer. Punch the peeled cured film with a punching machine to produce a test piece with a width of 3 mm and a sample length of 30 mm. For the obtained test piece, using a tensile testing machine (Tensilon), under the environment of crosshead speed 300mm/min, 25°C, 65%RH (relative humidity), in accordance with JIS-K6251 on the long side of the film The elongation at break of the film (elongation at break) was measured. In the evaluation, each Example or Comparative Example was implemented 5 times, and the arithmetic average of the measured values of the elongation at break in the 5 measurements was used as the index value. Regarding the above-mentioned index values, the evaluation was performed in accordance with the following evaluation criteria, and the evaluation results are described in Table 1. -Evaluation criteria- A: The above index value is more than 60%. B: The above index value is 55% or more and less than 60%. C: The above index value is 50% or more and less than 55%. D: The above index value is less than 50%.

From the above results, it can be seen that the curable resin composition containing the specific resin of the present invention is excellent in coatability. The comparative compositions of Comparative Examples 1 and 2 do not contain a specific resin. It can be seen that the comparative compositions of Comparative Examples 1 and 2 have poor coating properties.

<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 so that the film thickness was 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 in a nitrogen atmosphere to reach the temperature listed in the "hardening conditions" column of Table 1, and then heated at this temperature for 3 hours to form the interlayer for the rewiring layer. Insulating film. 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.

1: Silicon substrate 2: step difference A: The longitudinal length of the level difference B: The horizontal length of the step difference

Fig. 1 is a schematic diagram of a stepped substrate used in the embodiment.

Claims (14)

A curable resin composition, which contains: At least one resin having a polyalkyleneoxy group and a polymerizable group selected from the group consisting of polyimine and polyimine precursors; Polymerization initiator Polymerizable compound; and Solvent. The curable resin composition according to claim 1, wherein the structure having the polyalkoxyl group and the polymerizable group includes a structure represented by the following formula (1-1),

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site. The curable resin composition according to claim 2, wherein the Z ¹ as the polymerizable group includes at least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group. The curable resin composition according to claim 2 or claim 3, wherein the resin includes a structure represented by the aforementioned formula (1-1) as a structure represented by the following formula (1-2),

In formula (1-2), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linker, X ¹ represents the structure represented by the aforementioned formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and when there are multiple X ² , L ² , X ¹ or a, multiple X ² , L ² , X ¹ or a may be the same or different. The curable resin composition according to claim 2 or claim 3, which includes a repeating unit represented by the following formula (1-3) as a repeating unit including the structure represented by the aforementioned formula (1-1),

In formula (1-3), L ¹ represents a b+2 valent linking group, X ² represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L ² represents a single bond or a+1 valence Linking group, X ¹ represents the structure represented by the aforementioned formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L ⁴ represents the following formula (L4-1) or formula (L4-2) The indicated structure, when there are multiple X ² , L ² , X ¹ or a, the multiple X ² , L ² , X ¹ or a may be the same or different,

In formula (L4-1) or formula (L4-2), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or -NH-, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom Or monovalent organic group. The curable resin composition according to claim 4, wherein said L ¹ comprises a structure represented by at least one selected from the group consisting of structures represented by the following formulas (A-1) to (A-5) ,

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 bonding site ^{with X 2 in the aforementioned formula (1-2) or the aforementioned formula (1-3)} , 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, R ^A11 to R ^A14 , R ^A21 In ~R ^A24 , R ^A31 to R ^A38 , R ^A41 to R ^A48 and R ^A51 to R ^A58 , b is the bond ^{with X 2} in the aforementioned formula (1-2) or the aforementioned formula (1-3), respectively Location, * respectively and independently indicate the bonding location with other structures. 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 obtained by curing the curable resin composition according to any one of claims 1 to 7. A laminate having two or more layers of the cured film described in claim 8 and a metal layer between the cured films. A method for producing a cured film, which includes a film forming step of applying the curable resin composition according to any one of claims 1 to 7 to a substrate to form a film. The method for manufacturing a cured film according to claim 10, which includes an exposure step of exposing the aforementioned film and a development step of developing the aforementioned film. The method for producing a cured film according to claim 10 or claim 11, which includes the step of heating the film at 50°C to 450°C. A semiconductor device comprising the cured film described in claim 8 or the laminated body described in claim 9. A polyimide or polyimine precursor, which contains a structure represented by the following formula (1-1),

In formula (1-1), R ¹ each independently represents a hydrogen atom or an alkyl group, Z ¹ represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site.

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