TW202225227A - Resin composition, cured product, laminate, cured product production method, and semiconductor device - Google Patents

Abstract

A resin composition comprising a cyclic resin precursor and a compound A, which has a molecular weight of less than 1000 and comprises a plurality of polymerizable groups bonded by linking groups having at least one type of structure selected from the group consisting of cyclohexane structures and acetal structures; a cured product obtained by curing the resin composition; a laminate comprising the cured product; a method for producing the cured product; and a semiconductor device comprising the cured product and the laminate.

Description

Resin composition, cured product, laminate, method for producing cured product, and semiconductor element

The present invention relates to a resin composition, a cured product, a laminate, a method for producing the cured product, and a semiconductor element.

Cyclized resins such as polyimide have excellent heat resistance and insulating properties, and are therefore suitable for various applications. Although it does not specifically limit as said use, If the semiconductor element for actual mounting is mentioned as an example, the material of an insulating film or a sealing material, or use as a protective film can be mentioned. Moreover, it can also be used as a base film, a cover film, etc. of a flexible substrate.

For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of a cyclized resin such as a polyimide precursor. For example, by applying these resin compositions to a substrate by coating or the like to form a photosensitive film, and then exposing, developing, heating, etc. as necessary, a cured product can be formed on the substrate. The precursor of the cyclized resin such as the above-mentioned polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product. The curable resin composition can be applied by a known coating method, etc., so it can be said that the adaptability in manufacturing is excellent. For example, the applied resin composition has a high degree of freedom in designing the shape, size, and application position at the time of application. . In addition to the high performance possessed by cyclized resins such as polyimide, the industrial application development of the above-mentioned resin composition has been increasingly expected from the viewpoint of excellent suitability for production.

For example, Patent Document 1 describes a photosensitive resin composition comprising a photosensitive resin composition comprising as essential components polyamide and an isocyanuric acid derivative having a photopolymerizable unsaturated bond Among them, (A) the above-mentioned polyamide is a polyamide having a specific structural unit, (B) the above-mentioned isocyanuric acid derivative having a photopolymerizable unsaturated bond is a specific isocyanic acid derivative, The content of (B) relative to 100 parts by mass of (A) is 15 to 70 parts by mass. Patent Document 2 describes a monomer which has a Diels-Alder reaction site and at least one acryl group, and which can be polymerized by the acryl group.

[Patent Document 1] Japanese Patent Laid-Open No. 2007-241195 [Patent Document 2] Japanese Patent Laid-Open No. 2014-169384

In a cured product composed of a resin composition, it is required to improve the film strength (eg, elongation at break) of the obtained cured product.

An object of the present invention is to provide a resin composition excellent in film strength of the obtained cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a cured product containing the cured product or the semiconductor element of the above-mentioned laminate.

式（2-1）中，R ¹、R ²及R ³分別獨立地表示1價的有機基，R ¹、R ²及R ³中的至少1個含有具有聚合性基之基團。 ＜6＞如＜5＞所述之樹脂組成物，其中 上述R ²、R ³為具有由下述式（2-2）或下述式（2-3）中的任一個表示之部分結構之基團。 [化學式2]

式（2-2）、式（2-3）中，R ⁴分別獨立地表示氫原子或碳數1～5的烷基，*表示與式（2-1）中所包含之氧原子的鍵結部位，L表示2價的連接基。 ＜7＞如＜5＞所述之樹脂組成物，其中 上述由式（2-1）表示之化合物為由下述式（2-4）表示之化合物。 [化學式3]

式（2-4）中，R ⁴分別獨立地表示氫原子或碳數1～5的烷基，L表示2價的連接基。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其中 上述化合物A中的連接基含有具有交聯環結構或縮合環結構之環己烯結構。 ＜9＞如＜1＞至＜8＞之任一項所述之樹脂組成物，其中 上述化合物A包含由下述式（3-1）表示之化合物。 [化學式4]

式（3-1）中，R ¹、R ²分別獨立地表示1價的有機基，R ¹、R ²中的至少1個含有具有乙烯性不飽和鍵之基團。 ＜10＞如＜9＞所述之樹脂組成物，其中 上述由式（3-1）表示之化合物為由下述式（3-2）表示之化合物。 [化學式5]

式（3-2）中，R ³及R ⁴分別獨立地表示含有具有乙烯性不飽和鍵之基團之1價的有機基，L表示2價的連接基。 ＜11＞如＜1＞至＜10＞之任一項所述之樹脂組成物，其中 作為上述環化樹脂的前驅物含有聚醯亞胺前驅物。 ＜12＞如＜11＞所述之樹脂組成物，其中 上述聚醯亞胺前驅物具有由下述式（2）表示之重複單元， [化學式6]

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 ＜13＞如＜12＞所述之樹脂組成物，其中 上述式（2）中的R ¹¹³及R ¹¹⁴中的至少一者含有自由基聚合性基。 ＜14＞如＜1＞至＜13＞之任一項所述之樹脂組成物，其進一步含有自由基聚合起始劑。 ＜15＞如＜1＞至＜14＞之任一項所述之硬化性樹脂組成物，其用於形成再配線層用層間絕緣膜。 ＜16＞一種硬化物，其為硬化＜1＞至＜15＞之任一項所述之樹脂組成物而成。 ＜17＞一種積層體，其包含2層以上的由＜16＞所述之硬化物構成之層，在上述硬化物層之間的任一層之間包含金屬層。 ＜18＞一種硬化物的製造方法，其包括將＜1＞至＜15＞之任一項所述之樹脂組成物適用於基材上來形成膜之膜形成步驟。 ＜19＞如＜18＞所述之硬化物的製造方法，其包括選擇性地曝光上述膜之曝光步驟及使用顯影液顯影上述膜來形成圖案之顯影步驟。 ＜20＞如＜18＞或＜19＞所述之硬化物的製造方法，其包括在50～450℃下加熱上述膜之加熱步驟。 ＜21＞一種半導體元件，其含有＜16＞所述之硬化物或＜17＞所述之積層體。 [發明效果] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising: a compound A having a plurality of polymerizable groups bonded via a linking group having at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure and The molecular weight is less than 1000; and the precursor of the cyclized resin. <2> The resin composition according to <1>, wherein the polymerizable group in the compound A is a group having an ethylenically unsaturated bond. <3> The resin composition according to <1> or <2>, wherein the linking group in the compound A contains a plurality of at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure. <4> The resin composition according to any one of <1> to <3>, wherein the linking group in the compound A contains a plurality of cyclohexene structures or a plurality of acetal structures. <5> The resin composition according to any one of <1> to <4>, wherein the compound A contains a compound represented by the following formula (2-1). [Chemical formula 1]

In formula (2-1), R ¹ , R ² and R ³ each independently represent a monovalent organic group, and at least one of R ¹ , R ² and R ³ contains a group having a polymerizable group. <6> The resin composition according to <5>, wherein R ² and R ³ are those having a partial structure represented by either the following formula (2-2) or the following formula (2-3). group. [Chemical formula 2]

In formula (2-2) and formula (2-3), R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bond with an oxygen atom contained in formula (2-1) At the junction site, L represents a divalent linker. <7> The resin composition according to <5>, wherein the compound represented by the above formula (2-1) is a compound represented by the following formula (2-4). [Chemical formula 3]

In formula (2-4), R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group. <8> The resin composition according to any one of <1> to <7>, wherein the linking group in the compound A contains a cyclohexene structure having a cross-linked ring structure or a condensed ring structure. <9> The resin composition according to any one of <1> to <8>, wherein the compound A contains a compound represented by the following formula (3-1). [Chemical formula 4]

In formula (3-1), R ¹ and R ² each independently represent a monovalent organic group, and at least one of R ¹ and R ² contains a group having an ethylenically unsaturated bond. <10> The resin composition according to <9>, wherein the compound represented by the above formula (3-1) is a compound represented by the following formula (3-2). [Chemical formula 5]

In formula (3-2), R ³ and R ⁴ each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group. <11> The resin composition according to any one of <1> to <10>, wherein a polyimide precursor is contained as a precursor of the cyclized resin. <12> The resin composition according to <11>, wherein the polyimide precursor has a repeating unit represented by the following formula (2), [Chemical formula 6]

In formula (2), 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 hydrogen Atom or a monovalent organic group. <13> The resin composition according to <12>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the above formula (2) contains a radically polymerizable group. <14> The resin composition according to any one of <1> to <13>, which further contains a radical polymerization initiator. <15> The curable resin composition according to any one of <1> to <14>, which is used for forming an interlayer insulating film for a rewiring layer. <16> A cured product obtained by curing the resin composition according to any one of <1> to <15>. <17> A layered product comprising two or more layers composed of the cured product described in <16>, wherein a metal layer is included between any of the cured product layers. <18> A method for producing a cured product including a film forming step of applying the resin composition according to any one of <1> to <15> on a substrate to form a film. <19> The manufacturing method of the hardened|cured material as described in <18> which comprises the exposure process of selectively exposing the said film, and the developing process of developing the said film using a developing solution, and forming a pattern. <20> The manufacturing method of the hardened|cured material as described in <18> or <19> which comprises the heating process of heating the said film at 50-450 degreeC. <21> A semiconductor element comprising the cured product described in <16> or the laminated body described in <17>. [Inventive effect]

According to the present invention, a resin composition having excellent film strength of the obtained cured product, a cured product obtained by curing the aforementioned resin composition, a laminate containing the aforementioned cured product, a method for producing the aforementioned cured product, and the aforementioned cured product can be provided or the semiconductor element of the above-mentioned laminate.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. Regarding the description of a group (atomic group) in this specification, the descriptions that are not substituted and unsubstituted include both a group (atomic group) without a substituent and a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as the light used for exposure, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "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 means the total mass of the components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) were connected in series and used as a column to obtain the determination. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the washing liquid. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as a washing liquid, such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the standard layer among the plurality of layers concerned. That is, a third layer or a third element may be further interposed between the standard layer and the above-mentioned other layers, and the standard layer and the above-mentioned other layers may not be in contact with each other. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification may also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

(resin composition) The resin composition of the present invention contains: Compound A (hereinafter, also simply referred to as "compound A".) having a plurality of polymerizable groups bonded via a linking group including at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure and has a molecular weight of less than 1000; and Precursor of cyclized resin (hereinafter, also referred to as "specific resin").

The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used for forming a film for exposure and development using a developer containing an organic solvent. In addition, the resin composition of the present invention is preferably used for forming a photosensitive film for negative development. In the present invention, negative-tone development refers to development to remove non-exposed parts by development during exposure and development, and positive-tone development refers to development to remove exposed parts by development. As the method of the above-mentioned exposure, the above-mentioned developer, and the method of the above-mentioned development, for example, the exposure method described in the exposure step in the description of the manufacturing method of the cured product described later, and the developer and the development method described in the development step are used.

Regarding the resin composition of the present invention, the obtained cured product is excellent in film strength. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.

Conventionally, in the resin composition containing the precursor of the cyclized resin and the polymerizable compound, a step of cyclizing the precursor of the cyclized resin and polymerization of the polymerizable compound by heating or the like is performed to obtain a cured product. As a result of intensive research conducted by the present inventors, it was found that the higher the density of the cross-linked structure formed by the above-mentioned polymerization in the cured product, the lower the cyclization rate of the specific resin in the cured product. Membrane strength decreases. This is presumably because when the density of the above-mentioned crosslinked structure is too high, a structural change in the precursor of the cyclized resin is inhibited. It is considered that the inhibition of such a structural change is particularly significant when the polymerizable compound is polymerized by exposure or the like before heating. The resin composition of the present invention has a compound A having a plurality of polymerizable groups bonded via a linking group including at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight less than 1000. It is considered that the cyclohexene structure or the acetal structure is decomposed upon heating even if the above-mentioned compound A undergoes polymerization of the polymerizable group by, for example, exposure, heating, or the like. Therefore, it is considered that the structure change in the precursor of the cyclized resin is hardly hindered, and the cyclization rate of the specific resin in the cured product is increased, thereby improving the film strength of the cured product. In addition, it is considered that the cyclohexene structure or the acetal structure in the above-mentioned compound A is cut during heating, but after heating, for example, when cooled to room temperature (23° C.), a bond is formed again. Therefore, it is presumed that the cured product obtained from the resin composition of the present invention has a cyclized resin having a high cyclization rate in the cured product, and the density of the crosslinked structure is increased, so that it is also excellent in chemical resistance.

Here, Patent Documents 1 to 2 do not describe resin compositions containing Compound A and a precursor of a cyclized resin.

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

<Compound A> The resin composition of the present invention contains a compound A having a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight less than 1000. The molecular weight of compound A is less than 1000, preferably less than 900, more preferably less than 800. Although the lower limit of the said molecular weight is not specifically limited, For example, 200 or more is preferable.

[Polymerizable group] The polymerizable group contained in the compound A is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, and the like, and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an oxymethyl group, an epoxy group, an oxetanyl group, and a benzoxane. An azole group, a blocked isocyanate group, an amine group, and a group having an ethylenically unsaturated bond are preferred. Examples of the group having an ethylenically unsaturated bond include groups in which a vinyl group is directly bonded to an aromatic ring, such as (meth)acryloyloxy, (meth)acrylamido, and vinylphenyl groups. groups, allyl groups, vinyl groups, etc., and (meth)acryloyloxy is preferred from the viewpoint of reactivity.

Compound A contains a plurality of polymerizable groups. Compound A may contain, for example, one epoxy group and one (meth)acryloyloxy group, two or more types of polymerizable groups so as to be plural in total, but plural groups having ethylenic unsaturation are contained. Bonded groups are preferred.

The number of polymerizable groups in compound A may be 2 or more, preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 4, and particularly preferably 2. The molar amount of the polymerizable group contained in 1 g of Compound A is preferably 1.0 mmol/g or more, more preferably 1.5 mmol/g or more, and even more preferably 2.0 mmol/g or more. The upper limit of the molar amount is not particularly limited, but is preferably 8.0 mmol/g or less.

[Linking base] Compound A has a plurality of polymerizable groups bonded via a linking group including at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure. That is, in compound A, a plurality of polymerizable groups are bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure.

Preferably, the linking group contains at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and more preferably contains a plurality of cyclohexene structures or a plurality of acetal structures. The number of at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure in the above-mentioned linking group is preferably 1-10, more preferably 1-4, and even more preferably 1-3 Good, 2 is excellent.

The above-mentioned linking group is formed by at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure and a structure selected from the group consisting of a hydrocarbon group that may be substituted, a (poly) alkaneoxy group, -O-, -S A group formed by a combination of at least one group from the group of -, -SO ₂ -, -CO- and -NHCO- is preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination of these, and groups represented by a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these. for better. Moreover, as a substituent in the said hydrocarbon group, halogen atoms, such as a fluorine atom, are mentioned. Examples of the alkylene group in the (poly)alkeneoxy group include ethylidene, propylidene, trimethylene, and butylene, and ethylidene or propylidene is preferred. The above-mentioned linking group may be a linking group having a valence of 2 or more, preferably a linking group having a valence of 2 to 6, more preferably a linking group of a valence of 2 to 4, and more preferably a linking group of a divalent valence.

As the acetal structure or cyclohexene structure in the above-mentioned linking group, a structure cut at 120°C to 230°C is preferable, and a structure cut at 130°C to 200°C is more preferable.

式（2-1）中，R ¹、R ²及R ³分別獨立地表示1價的有機基，R ¹、R ²及R ³中的至少1個含有具有聚合性基之基團。 When the above-mentioned linking group contains an acetal structure, it is preferable that the compound A contains a compound represented by the following formula (2-1). [Chemical formula 7]

In formula (2-1), R ¹ , R ² and R ³ each independently represent a monovalent organic group, and at least one of R ¹ , R ² and R ³ contains a group having a polymerizable group.

In formula (2-1), as R ¹ , a hydrocarbon group is preferable, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an aralkyl group is more preferable, and an alkyl group is particularly preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is further preferable. As the aryl group, an aryl group having 1 to 20 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable. Moreover, it is preferable that the said aryl group is an aromatic hydrocarbon group. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable. As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 4 carbon atoms is more preferable. The preferable aspect of the alkyl moiety and the aryl moiety in the said aralkyl group is the same as the preferable aspect of the said alkyl group and aryl group.

式（P-1）中，L ¹表示n+1價的連接基，P ¹表示聚合性基，n表示1以上的整數，*表示與式（2-1）中的氧原子的鍵結部位。 式（P-1）中，作為L ¹，可舉出在上述連接基中說明之基團，較佳的態樣亦相同。 式（P-1）中，作為P ¹，可舉出在上述聚合性基中說明之基團，較佳的態樣亦相同。 式（P-1）中，n為1～10的整數為較佳，1～5的整數為更佳，1或2為進一步較佳，1為特佳。 當R ²或R ³不是具有聚合性基之基團之情況下，R ²或R ³與上述式（2-1）中的R ¹相同，較佳的態樣亦相同。 In formula (2-1), it is preferable that R ² and R ³ are each independently a group having a polymerizable group. When R ² or R ³ is a group having a polymerizable group, it is preferable that R ² or R ³ is a group represented by the following formula (P-1). [Chemical formula 8]

In formula (P-1), L ¹ represents an n+1-valent linking group, P ¹ represents a polymerizable group, n represents an integer of 1 or more, and * represents a bonding site to an oxygen atom in formula (2-1) . In the formula (P-1), as L ¹ , the groups described above for the linking group can be mentioned, and the preferred aspects are also the same. In the formula (P-1), as P ¹ , the groups described in the above-mentioned polymerizable groups can be mentioned, and the preferred aspects are also the same. In formula (P-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 or 2, and particularly preferably 1. When R ² or R ³ is not a group having a polymerizable group, R ² or R ³ is the same as R ¹ in the above-mentioned formula (2-1), and the preferred aspects are also the same.

式（2-2）或式（2-3）中，R ⁴分別獨立地表示氫原子或碳數1～5的烷基，*表示與式（2-1）中所包含之氧原子的鍵結部位，L表示2價的連接基。 式（2-2）或式（2-3）中，R ⁴為氫原子或甲基為較佳。 式（2-2）或式（2-3）中，作為L，可舉出在上述連接基中說明之基團，較佳的態樣亦相同。 Among these, it is preferable that R ² and R ³ are each independently a group having a partial structure represented by either the following formula (2-2) or the following formula (2-3), and R ² It is more preferable that one of and R ³ is a group having a partial structure represented by formula (2-2), and the other is a group having a partial structure represented by formula (2-3). [Chemical formula 9]

In formula (2-2) or formula (2-3), R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bond with an oxygen atom contained in formula (2-1) At the junction site, L represents a divalent linker. In formula (2-2) or formula (2-3), R ⁴ is preferably a hydrogen atom or a methyl group. In the formula (2-2) or the formula (2-3), as L, the groups described above for the linking group can be mentioned, and the preferred aspects are also the same.

式（2-4）中，R ⁴分別獨立地表示氫原子或碳數1～5的烷基，L表示2價的連接基。 式（2-4）中，R ⁴為氫原子或甲基為較佳。 式（2-4）中，作為L，可舉出在上述連接基中說明之基團，伸烷基、伸烷氧基或基於該等的組合之基團為更佳。 作為上述伸烷基，碳數2～10的伸烷基為較佳。 作為上述伸烷氧基，乙烯氧基為較佳。 The compound represented by the formula (2-1) is preferably a compound represented by the following formula (2-4). [Chemical formula 10]

In formula (2-4), R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group. In formula (2-4), R ⁴ is preferably a hydrogen atom or a methyl group. In formula (2-4), as L, the groups described in the above-mentioned linking group can be mentioned, and groups based on an alkylene group, an alkaneoxy group, or a combination thereof are more preferable. As said alkylene group, the C2-C10 alkylene group is preferable. As the above-mentioned alkyleneoxy group, vinyloxy group is preferable.

When the above-mentioned linking group in compound A contains a cyclohexene structure, it is preferable that the above-mentioned linking group in compound A contains a cyclohexene structure having a cross-linked ring structure or a condensed ring structure. The cyclohexene structure having a crosslinked ring structure or a condensed ring structure is particularly limited, and the following structures are exemplified. In the following structures, * represents a bond site with other structures, respectively. [Chemical formula 11]

式（3-1）中，R ¹及R ²分別獨立地表示1價的有機基，R ¹及R ²中的至少1個含有具有乙烯性不飽和鍵之基團。 Among these, it is preferable that the compound A contains a compound represented by the following formula (3-1). [Chemical formula 12]

In formula (3-1), R ¹ and R ² each independently represent a monovalent organic group, and at least one of R ¹ and R ² contains a group having an ethylenically unsaturated bond.

In the formula (3-1), as a preferable group for R ¹ or R ² , the same groups as the preferable group for R ² in the above-mentioned formula (2-1) can be mentioned.

式（3-2）中，R ³及R ⁴分別獨立地表示含有具有乙烯性不飽和鍵之基團之1價的有機基，L表示2價的連接基。 The compound represented by the formula (3-1) is preferably a compound represented by the following formula (3-2). [Chemical formula 13]

In formula (3-2), R ³ and R ⁴ each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group.

In formula (3-2), it is preferable that R ³ and R ⁴ are groups represented by the above formula (P-1). In the formula (3-2), as L, the groups described in the above-mentioned linking group can be mentioned, and an alkylene group, a polyalkeneoxy group, or a group based on a combination thereof are more preferable. As said alkylene group, the C2-C10 alkylene group is preferable. As said polyalkeneoxy group, a polyvinyloxy group is preferable. The repeating number of the above-mentioned polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4.

Specific examples of compound A include the following compounds, but are not limited thereto. [Chemical formula 14]

It is preferable that content of compound A exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

＜Specific resin＞ The resin composition of the present invention contains a precursor (specific resin) of a cyclized resin. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain represents the relatively longest bonding chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyimide, and the like. The precursor of the cyclized resin refers to the resin which becomes the cyclized resin by the change of the chemical structure by the external stimulus. And the resin which forms a ring structure and becomes a cyclized resin is more preferable. As a precursor of a cyclized resin, a polyimide precursor, a polybenzoxazole precursor, a polyimide imide precursor, etc. are mentioned. That is, the resin composition of the present invention contains as a specific resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide. At least one resin (specific resin) in the group of imide imide precursors is preferred. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, and more preferably contains a radical polymerization initiator described later and a radical crosslinking agent described later. . Moreover, as needed, the sensitizer mentioned later can be contained. For example, a negative photosensitive film can be formed from the resin composition of the present invention. In addition, the specific resin may have a polarity inversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the resin composition of this invention contains the photoacid generator mentioned later. From the resin composition of the present invention, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film can be formed. Moreover, it is preferable that the specific resin contains the group which can react with the polymerizable group contained in the compound A, and can bond covalently. For example, when the compound A contains a group having an ethylenically unsaturated bond, it is preferable that the specific resin also contains a group having an ethylenically unsaturated bond. Moreover, when compound A contains an epoxy group, it is preferable that a specific resin also contains an epoxy group. From the above aspect, it is considered that a crosslink is also formed between the compound A and the specific resin, and the chemical resistance of the obtained cured product is further improved.

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 15]

In formula (2), 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 hydrogen Atom or a monovalent organic group.

A ¹ and A ² in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R ¹¹¹ in formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond and may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a group including a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine of the group is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.

式中，A表示單鍵或2價的連接基，單鍵或選自可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等的組合中之基團為較佳，單鍵、選自可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [Chemical formula 16]

In the formula, A represents a single bond or a divalent linking group, and the single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- , -SO ₂ -, -NHCO- or a combination of these groups are preferred, single bond, selected from alkylene with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C ( The group in =O)-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C (CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of the diamine include the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl ring Hexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylene and 3,3-diaminodiphenylene, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diphenyl ether Aminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 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)hexa Fluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino- 4-Hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl] bis[4-(3-aminophenoxy)phenyl] bis[4-(2-aminophenoxy) base) phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4 '-Diaminodiphenylene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-amine) phenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) base)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4 ,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9 ,9'-bis(4-aminophenyl) fluoride, 4, 4'-dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- Diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine , 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2 ,7-Diamino pyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, ester of diaminobenzoic acid, 1, 5-Diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminobenzene) oxy)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]hexafluoro Propane, 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, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl 4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylene, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl ] Hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl) ) at least one diamine among biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetrabiphenyl.

Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.

Moreover, the diamine which has two or more alkylene glycol units described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain can also be preferably used.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO- which may be substituted by a fluorine atom. Or a combination of two or more of the above. Preferably, Ar is a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ - which may be substituted by a fluorine atom. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示式（2）中的與氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價的有機基，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 【化學式18】

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示式（2）中的與氮原子的鍵結部位。 作為提供式（51）或式（61）的結構之二胺，可舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 Moreover, from the viewpoint of i-ray transmittance, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 17]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * The bonding sites to the nitrogen atom in the formula (2) are each independently represented. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 6), an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1-6) fluorinated alkyl groups, etc. [Chemical formula 18]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2). 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned as the diamine which provides the structure of formula (51) or formula (61). Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

式（5）中，R ¹¹²為單鍵或2價的連接基，單鍵或選自可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等的組合中之基團為較佳，單鍵、選自可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及SO ₂-中之基團為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中之2價的基團為進一步較佳。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 19]

In formula (5), R ¹¹² is a single bond or a divalent linking group, and the single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms that may be substituted by fluorine atoms, -O-, -CO-, -S- , -SO ₂ - and -NHCO- and the groups in their combination are preferred, single bond, selected from alkylene with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO- , -S- and SO ₂ - are more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, A divalent group in the group of -S- and -SO ₂ - is more preferable.

式（O）中，R ¹¹⁵表示4價的有機基。R ¹¹⁵的較佳的範圍的含義與式（2）中之R ¹¹⁵的含義相同，較佳的範圍亦相同。 Specific examples of R ¹¹⁵ include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to R ¹¹⁵ , or may contain two or more types of tetracarboxylic dianhydride residues. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 20]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The meaning of the preferable range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferable range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone 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'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6, 7-Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2 ,3-dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4, 4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10- Perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4- Benzenetetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned as a preferable example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, as R ¹¹¹ , the residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxy group. Moreover, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, or the like, a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an oxymethyl group, an epoxy group, an oxetanyl group, and a benzoxane. azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, vinyl group) phenyl, etc.), (meth)acrylamido group, (meth)acryloyloxy group, group represented by the following formula (III), etc., the group represented by the following formula (III) is relatively good.

[Chemical formula 21]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group or a polyalkeneoxy group. Examples of preferable R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecylene and the like. Alkyl, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH) CH ₂ -, polyalkyleneoxy, ethylidene, propylidene, etc. alkylene, - CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkylene are more preferred, and alkylene such as ethylidene and propylidene or polyalkylene are further preferred. In the present invention, the polyalkeneoxy group refers to a group obtained by directly bonding two or more alkaneoxy groups. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, it is preferable that the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of Groups obtained by bonding propyleneoxy groups are preferred, polyvinyloxy groups or polypropyleneoxy groups are more preferred, and polyvinyloxy groups are further preferred. In the group obtained by bonding a plurality of vinyloxy groups and a plurality of acryloxy groups above, the vinyloxy groups and the acryloxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in patterns such as alternating . Preferred embodiments of the repeating numbers such as vinyloxy in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylaminopropyl methacrylate is mentioned.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity inversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specifically, as the diamine, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基，R ¹¹³及R ¹¹⁴中的至少一者為包含聚合性基之基團，兩者含有聚合性基為較佳。 It is preferable that the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By containing the repeating unit represented by the formula (2-A) in the polyimide precursor, the width of the exposure latitude can be wider. Formula (2-A) [Chemical Formula 22]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both of them contain a polymerizable group.

The meanings of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as those of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. . The meaning of R ¹¹² is the same as that of R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by the formula (2), or may contain two or more types. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, except that all repeating units in the polyimide precursor except for the terminal may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. Furthermore, when the resin composition includes a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.

式（3）中，R ¹²¹表示2價的有機基，R ¹²²表示4價的有機基，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] Although the structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 23]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), respectively, and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a linear or branched (preferably linear) aliphatic group is The dicarboxylic acid formed with 2 -COOH is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and 5 ~10 is excellent. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. , tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoro Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methyl Glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctane Diacid, azelaic acid, sebacic acid, hexafluorodecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, behenanedioic acid , tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, hexadecanedioic acid, nonacosanedioic acid, triacosanedioic acid, three Undecanedioic acid, tridocosanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulae, and the like.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [Chemical formula 24]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As a dicarboxylic acid containing an aromatic group, the following dicarboxylic acid which has an aromatic group is preferable, and the following dicarboxylic acid which consists only of the group which has an aromatic group and two -COOH is more preferable.

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-之群組中之2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 25]

In the formula, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ A divalent group in the group of -, * each independently represents a bonding site with other structures.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the meaning is the same as that of R ¹¹⁵ in the above formula (2), and the preferred range is also the same. R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-diaminophenol. Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- 3-Hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 ,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

式中，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²係由上述式表示之結構亦較佳。當R ¹²²為由上述式表示之結構時，在共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且其他2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 26]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. In addition, the structure in which R ¹²² is represented by the above formula is also preferable. When R ¹²² is a structure represented by the above formula, out of a total of 4 * and #, any two are a bonding site with a nitrogen atom to which R ¹²² in the formula (3) is bonded, and the other two are with The bonding site of the oxygen atom bonded by R ¹²² in the formula (3) is preferably, two * are the bonding sites with the oxygen atom bonded by R ¹²² in the formula (3), and the two # are The bonding site with the nitrogen atom bonded to R ¹²² in the formula (3), or two * are the bonding sites with the nitrogen atom bonded with R ¹²² in the formula (3) and two # are with The bonding site of the oxygen atom bonded by R ¹²² in the formula (3) is more preferable, and two * are the bonding sites with the oxygen atom bonded by R ¹²² in the formula (3), and the two # are The bonding site to the nitrogen atom to which R ¹²² in the formula (3) is bonded is further preferable.

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 27]

In formula (As), R ₁ is hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or selected from the following formula An organic group in the group of (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示鍵結於由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環。） [Chemical formula 28]

(In the formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, on R ₃ , brings the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it is considered to be a cause of high cyclization rate when hardened at low temperature. It is particularly preferable from the viewpoint that the effect is further improved.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the effects of high transparency to i-rays and high cyclization rate during curing at low temperature are maintained, which is preferable.

In addition, in the above formula (As), it is more preferable that R ₁ is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms. -CH ₂ - and -CH(CH ₃ )- have the effect of high cyclization rate at the time of lower hardening, and can obtain a polybenzoxazole precursor excellent in balance with sufficient solubility to a solvent. , -C(CH ₃ ) ₂ - is better.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Laid-Open No. 2013-256506. The contents are incorporated into this manual.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also contain other kinds of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the generation of warpage accompanying ring closure can be suppressed.

式（SL）中，Z具有a結構和b結構，R ^1s為氫原子或碳數1～10的烴基，R ^2s為碳數1～10的烴基，R ^3s、R ^4s、R ^5s、R ^6s中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。 [Chemical formula 29]

In formula (SL), Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R ^2s is a hydrocarbon group with 1 to 10 carbon atoms, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and a+b is 100 mol %.

In the formula (SL), as preferable Z, those in which R ^5s and R ^6s in the structure b are phenyl groups are exemplified. Furthermore, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating structural unit good. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, 2.3 or less is further preferable, and 2.2 or less is preferable for further better. In addition, when the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polybenzoxazole precursor are within the above-mentioned ranges. good. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.

式（PAI-2）中，R ¹¹⁷表示3價的有機基，R ¹¹¹表示2價的有機基，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價的有機基。 [Polyamide imide precursor] The polyamide imide precursor preferably contains a repeating unit represented by the following formula (PAI-2). 【Chemical formula 30】

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by connecting two or more, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, An aromatic group with 6-20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, an aromatic group with a carbon number of 6-20 or a single bond or a group obtained through a linking group A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these are bonded The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. A (ditrifluoromethyl)methylene group etc. are mentioned as an example of a preferable halogenated alkylene group. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two carboxyl groups among the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamidoimide precursor, a branched aliphatic, cyclic, or aromatic tricarboxylic acid compound, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.

Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, A tricarboxylic acid compound of an aromatic group with 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group or a single bond with a carbon number of 6 to 20 is included. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group is more preferable.

In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (eg, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (eg, trimellitic anhydride ammonium chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in the above formula (2), respectively, and the preferred aspects are also the same.

The polyamidoimide precursor may further contain other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [Chemical formula 31]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by connecting two or more, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, An aromatic group with 6-20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, an aromatic group with a carbon number of 6-20 or a single bond or a group obtained through a linking group A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these are bonded The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. A (ditrifluoromethyl)methylene group etc. are mentioned as an example of a preferable halogenated alkylene group. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, a single bond, or a dicarboxylic acid compound or a dicarboxylic acid dihalide of a group obtained by combining two or more of these groups through a linking group is relatively Preferably, a dicarboxylic acid compound or dicarboxylic acid dihalogenation containing an aromatic group with a carbon number of 6 to 20 or a single bond or a group obtained by combining two or more aromatic groups with a carbon number of 6 to 20 through a linking group Things are better.

Moreover, as a specific example of a dicarboxylic acid compound, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.

In the formula (PAI-1), the meaning of R ¹¹¹ is the same as that of R ¹¹¹ in the above-mentioned formula (2), and the preferred aspects are also the same.

Moreover, it is also preferable that the polyamide imide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyamide imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, the polyamide imide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesiveness with the substrate. Specifically, examples of using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned as the diamine component.

As one embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) can be mentioned. Indicates that the total content of repeating units is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminal may be repeating units represented by formula (PAI-2), and may be represented by formula (PAI-1) Any one of the repeating unit of and the repeating unit represented by formula (2). Moreover, as another embodiment of the polyamide imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned In the form of more than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminal may be repeating units represented by formula (PAI-2) or by formula (PAI-1) any of the repeating units.

The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable. The molecular weight of the polyamide imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the resin composition includes a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges is better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imide precursors as one resin are respectively within the above-mentioned ranges.

[Production method of polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and obtaining polyamide by reacting tetracarboxylic dianhydride and diamine at low temperature Amino acid and method for esterification using a condensing agent or alkylating agent, a method for obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting with a diamine in the presence of a condensing agent, by tetracarboxylic dianhydride and alcohol to obtain a diester, then use a halogenating agent acid to halogenate the remaining dicarboxylic acid and react with a diamine, etc. Among the above-mentioned production methods, a method in which the remaining dicarboxylic acid is acid-halogenated with a halogenating agent after obtaining a diester from a tetracarboxylic dianhydride and an alcohol and reacted with a diamine is more preferable. Examples of the above-mentioned condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-Carbonyldioxy-bis-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionite chloride, oxalyl chloride, phosphorus oxychloride, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is performed. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diglyme (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. ester, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazbicyclo[5.4.0]undec-7-ene, N,N-di Methyl-4-aminopyridine, etc.

-Capping agent- When producing a polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the residual carboxylic acid anhydride, acid anhydride derivative, or amine group at the resin end of the polyimide precursor or the like. When sealing the carboxylic acid anhydride and acid anhydride derivative remaining at the resin end, as the end-capping agent, monoalcohol, phenol, thiol, thiophenol, monoamine, etc., are used. Alcohols, phenols or monoamines are more preferred. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2- Primary alcohols such as chloromethanol, furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butanol, adamantane alcohol and other tertiary alcohols grade alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as the preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol are preferred. Two or more kinds of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end-capping agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred end-capping agent for the amine group is carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., carboxylic acid anhydride, carboxylic acid chloride are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3- Dicarboxylic anhydrides, etc. Moreover, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, neopentyl chloride, cyclohexane methyl chloride, 2-ethylhexyl chloride can be mentioned. Acyl chloride, cinnamon chloride, 1-adamantane methyl chloride, heptafluorobutane chloride, stearyl chloride, benzyl chloride, etc.

-Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof, and the polymerization is precipitated. A polyimide precursor or the like can be obtained by precipitating the material component as a solid and drying it. In order to improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. In addition, a step of removing ionic impurities using an ion exchange resin may also be included.

〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, and 50 mass % with respect to the total solid content of the resin composition. The above is further preferred. Moreover, the content of the resin in the resin composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % or less with respect to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin. Specifically, the resin composition of the present invention may contain a total of two or more types of specific resins and other resins described later, may contain two or more types of specific resins, and preferably contains two or more types of specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures (R ¹¹⁵ in the above-mentioned formula (2)) derived from dianhydrates are contained. is better.

<Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, and urethane resins , butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 ^-3 ) molar/g or more) (meth)acrylic resin is added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (hardened product), and the like.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more with respect to the total solid content of the resin composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, more preferably 70 mass % or less, and 60 mass % or less with respect to the total solid content of the resin composition. It is still more preferable that it is not more than 50 mass %, and it is still more preferable that it is not more than 50 mass %. Moreover, as a preferable aspect of the resin composition of this invention, the aspect in which content of another resin is a low content can also be used. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<Polymerizable compound> It is preferable that the resin composition of this invention contains a polymerizable compound. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acryloyl group Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (hardened product), the resin composition of the present invention may also include a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. better.

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

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and hydrogen thio groups and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. , Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions of paragraphs 0113 to 0122 of JP 2016-027357 A, which are incorporated in the present specification.

Moreover, it is also preferable that the radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane etc. Compounds obtained by adding ethylene oxide or propylene oxide to alcohol followed by (meth)acrylic esterification, such as Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication Sho 51 - Urethane (meth)acrylates described in each publication No. 037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 Polyester acrylates, epoxy acrylates and other polyfunctional acrylates or methacrylates and mixtures thereof as the reaction product of epoxy resin and (meth)acrylic acid. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making a compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

Moreover, as preferable radical crosslinking agent substances other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. A compound having a perylene ring and having two or more groups with an ethylenically unsaturated bond or a cardo resin.

Furthermore, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. Sho 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, or Japanese Patent Publication No. Hei 02 can also be cited. - Vinylphosphonic acid-based compounds and the like described in Gazette No. 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. incorporated into this manual.

In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds, which are described as formula (1) and formula (2) together with specific examples thereof, can also be used as a radical crosslinking agent in a polyfunctional alcohol. A compound obtained by adding ethylene oxide or propylene oxide and then (meth)acrylated.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as the radical crosslinking agent, and these contents are incorporated in the present specification.

As a radical crosslinking agent, dipeotaerythritol triacrylate (a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (a commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipivaloerythritol penta(meth)acrylate (commercially available as KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

Commercially available products of the radical crosslinking agent include, for example, SR-494 manufactured by Sartomer Company, Inc. which is a tetrafunctional acrylate having four vinyloxy chains, and SR-494, which is a bifunctional acrylate having four vinyloxy chains. Methacrylates SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentenyloxy chains, as a TPA-330, 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 the radical crosslinking agent, for example, the amino groups described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Ethyl formate acrylates, those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have ethylene oxide. Urethane compounds with an alkane-based skeleton are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., LTD., for example.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, difunctional acrylate with other urethane bonds, with urethane Bifunctional methacrylate of ester bond. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (hardened product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred. In addition, as a bifunctional or more radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types together, it is preferable that the total amount is in the said range.

[Other cross-linking agents] It is also preferable that the resin composition of the present invention contains other cross-linking agents different from the above-mentioned radical cross-linking agents. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned radical cross-linking agents, and have a plurality of cross-linking agents in the molecule that are promoted to interact with the composition by the photosensitive photoacid generator or photobase generator. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of methylol and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and contains a compound selected from the group consisting of the glycoluril-based crosslinking agent described below. and at least one compound in the group of melamine-based crosslinking agents is more preferred.

As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group is directly on the nitrogen of the aromatic group or the following urea structure. Compounds substituted on atoms or on tris are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[Chemical formula 32]

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include various compounds of the following general formula.

[Chemical formula 33]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R ⁵ represents a group that can be removed by the action of an acid.)). R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R ⁵ in the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that is released by the action of an acid, and the group represented by -C(R ⁴ ) ₂ COOR ⁵ can be exemplified. Out-C(R ₃₆ )(R ₃₇ )(R ₃₈ ),-C(R ₃₆ )(R ₃₇ )(OR ₃₉ ),-C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted by an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. In addition, these groups may further have known substituents within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As a group to be decomposed by the action of an acid to generate an alkali-soluble group or a group to be released by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, and the like are preferable. Further preferred are tertiary alkyl ester groups and acetal groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an aryloxymethyl group, the compound which changed the alkoxymethyl group of the following compound to an aryloxymethyl group can be mentioned. Although the following various compounds can be mentioned as a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, it is not limited to these.

[Chemical formula 34]

[Chemical formula 35]

As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethyl methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril based cross-linking agents such as glycoluril; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc., Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents; Monomethylolated Propylene Urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it can also be preferably used to directly bond to an aromatic ring (preferably a benzene ring). A compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

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

Furthermore, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds and benzoxanthine compounds as other crosslinking agents.

-Epoxy compounds (compounds with epoxy groups)- As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature hardening and warpage of the resin composition of the present invention.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy epoxy silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but 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) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (product names above, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD ( Registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (product names above, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[Chemical formula 36]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

Among the above-mentioned structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

-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-hydroxymethoxy oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-Benzoxazole compounds (compounds having a benzoxazolyl group)- Due to the cross-linking reaction caused by the ring-opening addition reaction, the benzoxazine compound does not generate outgassing during hardening, thereby further reducing thermal shrinkage and suppressing the generation of warpage, so it is preferable.

Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine, (the above are the product names, manufactured by Shikoku Chemicals Corporation), and benzoxazine of polyhydroxystyrene resin. Adduct, novolac-type dihydrobenzoxazine compound. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and 1.0 to 10 mass % relative to the total solid content of the resin composition of the present invention. Mass % is particularly good. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

[Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Preferably, the polymerization initiator is a radical polymerization initiator. The radical polymerization initiator is not particularly limited, and can be appropriately selected from known radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active free radicals by some action with the sensitizer of photoexcitation.

Preferably, the photo-radical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L･mol ^-1 ･cm ^-1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated in the present specification. In addition, Japanese Patent Laid-Open No. 2014-130173, Paragraphs 0065 to 0111, the compounds described in Japanese Patent No. 6301489, and the compounds described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019 Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in Gazette No. 2019-044030, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Application Laid-Open No. 2019-167313, These contents are also incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated in the present specification. Among the commercially available products, KAYACURE-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. incorporated into this manual.

As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: all made by BASF).

As the α-amino ketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all product names: BASF Corporation) can be used system).

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength is matched to a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in this specification.

As an acyl phosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.

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

Specific examples of the oxime compound include the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 A Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in JP 2000-066385 A, the compound described in JP 2004-534797, JP 2017-019766 A Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Laid-Open No. 2017-198865 The compounds described in WO 2017/164127, the compounds described in paragraphs 0025 to 0038 of WO 2017/164127, the compounds described in WO 2013/167515, etc., are incorporated in the present specification.

Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 37]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photo-radical polymerization initiator 2) described in Gazette No. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), ADEKA ARKLSNCI-730, NCI-831, and ADEKA ARKLSNCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 38]

As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compound described in JP 2014-137466 A and the compound described in JP 06636081, the contents of which are incorporated in the present specification.

As the photoradical polymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, the contents of which are incorporated in the present specification.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. The compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471 are incorporated into the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound having a nitro group as a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A and 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A , The compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated into the present specification. Moreover, ADEKA ARKLSNCI-831 (made by ADEKA Corporation) can also be mentioned as an oxime compound which has a nitro group.

As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used. As these photopolymerization initiators, the compounds and the like described in International Publication No. WO 2019/088055 can be mentioned, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into an aromatic ring can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzyl group is still more preferable because it is easy to form a film having excellent light resistance. The benzyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkenyl group, alkylthio group, arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio group or an amine group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、膦醯基、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫烷基、芳基硫烷基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基。 其中，R ^X10～R ^X14中的至少一個為拉電子基團。 The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [Chemical formula 39]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphinyl group, carbamoyl group or sulfamoyl group, R ^X2 represents an alkyl group, an alkenyl group , alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl An acyl group, an arylsulfonyl group, an acyloxy group or an amine group, and R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent. Wherein, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X12 is an electron withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.

As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group described in JP-A No. 2009-191061 can be mentioned. etc., the contents are incorporated into this specification.

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

Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is still more preferable to use at least one compound in the group of ketone compounds, and it is still more preferable to use a metallocene compound or an oxime compound.

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

【Chemical formula 40】

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

[Chemical formula 41]

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

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in this specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can also be used. By using these photoradical polymerization initiators, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult with time, and the temporal stability of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The described oxime ester photoinitiator etc., the content is incorporated in this specification.

When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 30 mass % with respect to the total solid content of the resin composition of the present invention. 15 mass %, more preferably 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

[Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc. to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photo-radical polymerization initiator are decomposed by chemical change and generate radicals, acids or bases. As sensitizers that can be used, benzophenone-based, Michler's ketone-based, oxaphthalone-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, and anthraquinone-based sensitizers can be used , anthracene series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole methine Azo series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series and other compounds. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4' -diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin , 3-ethoxycarbonyl-7-diethylamino coumarin (7-(diethylamino) coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-Phenyldiethanolamine, N-p-Tolyldiethanolamine, N-Phenylethanolamine, 4-Mortholinyl benzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Amyl ester, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzoxazole Dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminostyryl)benzyl ) Styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. In addition, other sensitizing dyes can be used. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A, which are incorporated in the present specification.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. for further better. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH and GeH in the molecule can be used. Addition fragmentation chain scission transfer) polymerized dithiobenzoic acid, trithiocarbonate, dithiocarbamate, xanthate compound with thiocarbonylthio group. These can generate free radicals by supplying hydrogen to the less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.

In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO 2015/199219 can also be used, the contents of which are incorporated in the present specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention More preferably, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

[Photoacid generator] It is preferable that the resin composition of this invention contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating an acid by exposure to light is preferred. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives , Antimony derivatives, halogen peroxide, sulfonamides, etc.

As a photoacid generator used for the resin composition of this invention, a quinonediazide compound, an oxime sulfonate compound, an organic halogen compound, an organic borate compound, a dioxane compound, an onium salt compound etc. are mentioned, for example. From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of mechanical properties of the formed film, oxime esters are preferred.

Examples of the quinonediazide compound include a sulfonic acid ester of quinonediazide bonded to a monovalent or polyvalent hydroxy compound, and a sulfonic acid sulfonamide bond of quinonediazide to a monovalent or multivalent amine compound. On the other hand, those obtained are those obtained by the sulfonate bond of quinonediazide and/or the sulfonamide bond to the polyhydroxypolyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but on average, more than 40 mol% of the entire functional groups are substituted with quinonediazide as better. By containing such a quinonediazide compound, it is possible to obtain a resin composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tertiary butanol, cyclohexanol, naphthol, Bis-Z, and BisP. -EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P , BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF , TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethylacetate Oxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxydiol Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.

Specific examples of the amine compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc., but not limited on such.

Moreover, specific examples of the polyhydroxypolyamine compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like, but It is not limited to these.

Among these, it is preferable to contain a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. Resolution Thereby, higher sensitivity and higher resolution to i-ray exposure can be obtained.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed portion and the unexposed portion can be obtained, and thus higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is represented by the following formula (OS-1), formula (OS-103), formula (OS-104) or formula (OS-105) ) represented by oxime sulfonate compounds are preferred.

[Chemical formula 42]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X ³ exist, they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ³ may have a substituent. As the alkyl group in the aforementioned X ³ , a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of ^X3 may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In formula (OS-1), m3 is ³ , ^X3 is a methyl group, the substitution position of X3 is an ortho position, and ^R34 is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include those in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A. The following compounds are described, and these contents are incorporated into this specification.

[Chemical formula 43]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 which independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. Atom, sometimes there are plural R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl group represented by R ^s1 ( It is preferable to have 4 to 30 carbon atoms) within a range in which the effects of the present invention can be obtained, and may have a known substituent.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1-12) or an aryl group (preferably with a carbon number of 6-30), A hydrogen atom or an alkyl group is more preferable. In the compound sometimes more than two R ^s2 , one or two are preferably alkyl, aryl or halogen atom, one is alkyl, aryl or halogen atom is more preferably, one is alkyl and It is particularly preferred that the remainder be hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a known substituent within a range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is 2. good. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and is represented by the above formula (OS- 104) The compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 44]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms , methyl is particularly good.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Moreover, in the said oxime sulfonate compound, about the three-dimensional structure (E, Z) of an oxime, either may be sufficient as it, and a mixture may be sufficient as it. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP 2011-209692 A and JP 2015-194674 A. The compounds described in paragraphs 0168 to 0194 of the official gazette are incorporated into the present specification.

As another preferable aspect of the oxime sulfonate compound which contains at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 45]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group , cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, and an alkylcarbonyl group , arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring, respectively. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

作為市售品，能夠舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製）、MBZ-101（Midori Kagaku Co.,Ltd.製）等。 More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). Moreover, in the said oxime sulfonate compound, regarding the steric structure (E, Z, etc.) of an oxime or a benzothiazole ring, it may be any one of them, respectively, and a mixture may be sufficient as it. Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195-0207 of JP-A No. 2015-194674, These contents are incorporated into this specification. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 46]

As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 47]

Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, and Japanese Patent Laid-Open Publication No. 46-4605. Japanese Patent Laid-Open No. 48-36281, Japanese Patent Laid-Open No. 55-32070, Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 61-169837 Sho 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, the contents of which are incorporated into the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: a symmetrical triazole compound can be mentioned as a preferable example. More preferably, at least one mono-, di- or tri-halogen substituted methyl group is bonded to a symmetrical tris-tris-ring. Symmetrical tris-derivatives include, for example, 2,4,6-tri( Monochloromethyl)-Symmetrical Tris, 2,4,6-Tris(dichloromethyl)-Symmetrical Tris, 2,4,6-Tris(trichloromethyl)-Symmetrical Tris, 2-Methyl -4,6-Bis(trichloromethyl)-symmetric tris, 2-n-propyl-4,6-bis(trichloromethyl)-symmetric tris, 2-(α,α,β-trichloro Ethyl)-4,6-bis(trichloromethyl)-symmetric-tris, 2-phenyl-4,6-bis(trichloromethyl)-symmetric-tris, 2-(p-methoxyphenyl) )-4,6-bis(trichloromethyl)-symmetric tris𠯤, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-symmetric tris𠯤, 2-( p-Chlorophenyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6- Bis(trichloromethyl)-symmetric tris', 2-styryl-4,6-bis(trichloromethyl)-symmetric tris, 2-(p-methoxystyryl)-4,6- Bis(trichloromethyl)-symmetric tris𠯤, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-symmetric tris𠯤, 2-(p-tolyl)-4 ,6-bis(trichloromethyl)-symmetric tris-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (trichloromethyl)-symmetric tris-4, 2-phenylthio-4 ,6-bis(trichloromethyl)-symmetric tris(tris), 2-benzylthio-4,6-bis(trichloromethyl)-symmetric tris, 2,4,6-tris(dibromomethyl) -Symmetrical Tris, 2,4,6-Tris(tribromomethyl)-Symmetrical Tris, 2-Methyl-4,6-bis(Tribromomethyl)-Symmetrical Tris, 2-Methoxy- 4,6-bis(tribromomethyl)-symmetric tris𠯤, etc.

Examples of the organic borate compound include JP 62-143044 A, JP 62-150242 A, JP 9-188685 A, JP 9-188686 A, JP 9-188686 A Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98" .Proceeding April 19-22, 1998, Chicago" etc. The organoborates described in, Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Laid-Open No. 6-175561 Organoboronium complexes or organoboroxoperium complexes, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 9-188710 The organoboron phosphonium complexes described in Gazette No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-306527 Organoboron transition metal complex complexes, such as Japanese Patent Laid-Open No. 7-292014, etc., are taken as specific examples, and the contents thereof are incorporated in the present specification.

As the dibasic compound, the compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and the like, and diazodithio compounds can be mentioned.

Examples of the above-mentioned onium salt compounds include diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, 21,423 (1980), and U.S. Patent No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Patent No. 4,069,055, US Patent No. 4,069,056, European Patent No. 104,143, US Patent No. 339,049 No., each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, Permamate salts described in each specification of U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307(1977), Selenium salts, C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. Arsenic salts, onium salts such as pyridinium salts, and the like described in (1988) are incorporated into the present specification.

式（RI-I）中，Ar ₁₁表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₁₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar ₂₁、Ar ₂₂分別獨立地表示可以具有1～6個取代基的碳數1～20的芳基，作為較佳的取代基，可舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₂₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R ₃₁、R ₃₂、R ₃₃分別獨立地表示可以具有1～6個取代基之碳數6～20的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，芳基為較佳。作為較佳的取代基，可舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₃₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 As an onium salt, the onium salt represented by the following general formula (RI-I) - (RI-III) is mentioned. [Chemical formula 48]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferable. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkylamide group with 1 to 12 carbon atoms in the alkyl group Or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents and a carbon number of 6 to 20, preferably an alkyl group, an alkenyl group and an alkynyl group. , from the viewpoint of reactivity and stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. alkoxy group having 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom, monoalkylamine group having 1 to 12 carbon atoms, dialkylamine group having 1 to 12 carbon atoms each independently, Alkyl amido group or aryl amido group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, thioalkyl group having 1 to 12 carbon atoms Thioaryl. Z ₃₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

【化學式50】

【化學式51】

【化學式52】

As a specific example of a preferable photoacid generator, the following are mentioned. [Chemical formula 49]

【Chemical formula 50】

【Chemical formula 51】

【Chemical formula 52】

The photoacid generator is preferably used in 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % with respect to the total solid content of the resin composition. It is even more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. When using a plurality of types in combination, it is preferable that these total amounts are within the above-mentioned range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.

<Alkali Generator> The resin composition of the present invention may contain an alkali generator. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for the resin composition of this invention, a thermal alkali generator and a photobase generator are mentioned. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali generator. By including a thermal alkali generator in the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties or chemical resistance, for example, as a rewiring layer included in a semiconductor package The performance with the interlayer insulating film becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. 【Chemical formula 53】

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three 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 amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a condensed ring formed by condensing a monocyclic ring or two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexyl ring and a benzene ring, and more preferably a cyclohexyl ring.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or arane A base (preferably with a carbon number of 7 to 25, more preferably 7 to 19, and further preferably 7 to 12) is preferable. These groups may have a substituent within a 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 to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and more preferably 3 to 12). Preferably, a cycloalkyl group which may have a substituent (3-24 carbon atoms are preferable, 3-18 is more preferable, and 3-12 is further preferable) is more preferable, and a cyclohexyl group which may have a substituent is further preferable. good.

Examples of Rb ³ include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and an aryl group (preferably having 6 to 22 carbon atoms, and having 6 to 18 carbon atoms). is more preferred, 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 better, 7-19 is better, 7-12 is further better), aralkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), alkane Oxy group (preferably carbon number 1-24, more preferably 2-18, more preferably 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6- 12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), aralkenyl and aralkoxy are preferred. Rb ³ may have a substituent within the range in which the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 54]

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 formula (B1), respectively. Rb ¹³ is alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 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 are more preferable, and 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ¹³ is preferably an aralkyl group.

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

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

Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). 【Chemical formula 55】

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl group is preferred. Rb ¹⁷ is an alkyl group (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.

【Chemical formula 56】

In the formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 more than one. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In the present specification, "connection chain" refers to a chain of atoms connecting two atoms of a connection object or an atomic chain on a path between a group of connected atoms in the shortest (minimum number of atoms) manner to connect the connection objects. For example, in a compound represented by the following formula, L is constituted by a phenylene ethylidene group, and has an ethylidene group as a saturated hydrocarbon group, the linking chain is constituted by four carbon atoms, and the number of atoms on the path of the linking chain (that is, The number of atoms constituting the connecting chain, hereinafter also referred to as "the length of the connecting chain" or "the length of the connecting chain") is four. [Chemical formula 57]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). 【Chemical formula 58】

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking chain length is the number of atoms present in the arrangement of atoms that makes the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, and 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , since the basicity of the generated base is high, it is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of chain alkyl groups and cyclic alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, tertiary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. The group related to the combination of a chain alkyl group and a cyclic alkyl group includes, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, it is preferable that R ^N1 and R ^N2 are alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the bases generated by decomposition described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesiveness at the time of lamination with a metal (for example, copper).

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , imidazoline ring, pyrazolidine ring, piperidine ring, piperidine ring, endoline ring, etc., preferably pyrroline ring, pyrrolidine ring, piperidine ring, piperidine ring, endoline ring .

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.

Specific examples of the protecting group include a chain-like or cyclic alkyl group or a chain-like or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.

The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.

As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.

As the base generator, the following examples are given, but the present invention is not limited to these.

【Chemical formula 59】

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

Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. 【Chemical formula 60】

Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 61]

When the resin composition of the present invention contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

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

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucan ketone, and dihydrodextran Sugar ketones and the like are preferred.

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

As the sulfites, for example, dimethyl sulfite is mentioned as a preferable one.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formyl dimetholine, N-acetyl dimetholine, etc. are preferred.

Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., it is also preferable to mix two or more types.

In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone or a solvent consisting of two or more Mixed solvents are preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination or N-methyl-2-pyrrolidone and ethyl lactate in combination.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the resin composition of the present invention , it is more preferable to set it as an amount of 10-70 mass %, and it is still more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having a sulfonamide structure, compounds having thiourea, and phosphoric acid derivatives. Compounds, β-ketoester compounds, amine compounds, etc.

[Silane coupling agent] Examples of the silane coupling agent include compounds described in Paragraph 0167 of International Publication No. 2015/199219, compounds described in Paragraphs 0062 to 0073 of JP 2014-191002 A, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 are incorporated in the present specification. Moreover, 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 compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

【Chemical formula 62】

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based Adhesives] Examples of the aluminum-based adhesive agent include aluminum tris(ethylacetate)aluminum, tris(acetoacetone)aluminum, aluminum ethylacetate diisopropoxide, and the like.

In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the vulcanization described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, the contents of which are incorporated into this specification.

The content of the metal adhesion improver is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin . By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

<Migration inhibitor> Preferably, the resin composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions from the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetra azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, with sulfur Urea and hydrogen thio compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

Alternatively, an ion scavenger that captures 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 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 compounds, etc., the contents of which are incorporated in this specification.

Specific examples of the migration inhibitor include the following compounds.

[Chemical formula 63]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass % with respect to the total solid content of the resin composition of the present invention , 0.1 to 1.0 mass % is more preferable.

Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds Wait.

As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallophenol, p- Tertiary butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2 '-Methylene bis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-triamine tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso- 5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiary butyl) ) phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6 -(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1- Oxy radicals, phenothiazine, phenothiazine, 1,1-diphenyl-2-pyrrolehydrazine, copper(II) dibutyldithiocarbonate, nitrobenzene, N-nitroso-N- Phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, the contents of which are incorporated in the present specification.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0.02 to 15% by mass, more preferably 0.02 to 15% by mass relative to the total solid content of the resin composition of the present invention. 0.05-10 mass % is more preferable.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

＜Acid scavenger＞ It is preferable that the resin composition of this invention contains an acid scavenger in order to reduce the change in performance with time from exposure to heating. Among them, the acid scavenger refers to a compound capable of capturing an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amine, tertiary amine and ammonium salt are more preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and an alkylamine derivative having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid scavenger is an anion having a cation selected from the group consisting of ammonium, diazo, iodonium, perium, phosphonium, pyridinium and the like and an acid having a lower acidity than that generated by the acid generator. Salt is preferred.

As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium oxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, perium hydroxide having a 2-oxoalkyl group, and more specifically, hydrogen Triphenyl strontium oxide, tris(tertiary butylphenyl) strontium hydroxide, bis(tertiary butylphenyl) iodonium hydroxide, benzalkonium methylthiophenium hydroxide, 2-oxopropyl hydroxide Thiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. can be mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.

Specific examples of preferable acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, and cyclohexylmethylamine , cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine Amine, DBU (diazabicycloundec), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide , ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylamine Ethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, sperm triamine, diaminocyclohexane, bis(2-methoxyethyl)amine , piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline , phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, amino-endoline, amino-alkyl Morphine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually 0.001 to 10% by mass based on the total solid content of the composition. Preferably it is 0.01-5 mass %.

The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction of the resolution caused by the increase in thickness of the relief pattern with time after exposure to heat treatment , 300 or less is better. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium, as needed, within the range in which the effects of the present invention can be obtained. Compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (eg, defoaming agents, flame retardants, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 The descriptions in paragraphs 0101 to 0104, and paragraphs 0107 to 0109 are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the resin composition of the present invention.

[Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. . That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, the film formation of a small uniform thickness with uneven thickness can be performed more preferably.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used. incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and as a specific example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned, and these contents are incorporated in this specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a compound having two or more (preferably A repeating unit of a (meth)acrylate compound having 5 or more alkaneoxy groups (preferably vinyloxy groups, propenyloxy groups), and the following compounds can also be exemplified as the fluorine-based interface used in the present invention active agent. 【Chemical formula 64】

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated in the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.

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

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive performance Materials Inc.), KP-341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), and the like.

Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D -6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO., LTD.), etc.

As the nonionic surfactant, glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (TAKEMOTO Oil & FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (Nissin Chemical Co., Ltd.) and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.

Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention to make it non-uniform in the drying process after coating exist on the surface of the resin composition of the present invention.

In addition, the compound described in the paragraph 0155 of International Publication No. 2015/199219 can also be used as the higher fatty acid derivative, the content of which is incorporated in the present specification.

When the 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 resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. Also by adding a thermal radical polymerization initiator, since the resin and the polymerizable compound can be polymerized, the solvent resistance can be further improved. In addition, the above-mentioned photopolymerization initiator may have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated in the present specification.

When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The said average particle diameter of an inorganic particle is a primary particle diameter, and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tertiary butylphenyl salicylate, and the like, and examples of the benzophenone-based ultraviolet absorber include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, as an example of a benzotriazole type ultraviolet absorber, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tertiarybutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiary pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

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

As an organotitanium compound which can be used, the thing which an organic group couple|bonded with a titanium atom via a covalent bond or an ionic bond is mentioned. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the resin composition has excellent storage stability and can obtain a good hardened pattern, so the titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.

Among them, as the organotitanium compound, from the viewpoint of exerting better chemical resistance, it is selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound and III) titanocene compound At least one compound is preferred. In particular, bis(ethylacetate)titanium diisopropoxide, tetrakis(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the elongation property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiarybutyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tertiarybutyl-6-methyl) phenyl) etc. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO- 80 and Adekastab AO-330 (the above are made by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, the contents of which are incorporated in the present specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As potential antioxidants, compounds in which the site that acts as an antioxidant is protected by a protective group can be mentioned, and are prepared by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst. A compound that acts as an antioxidant when heated to remove the protecting group. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Laid-Open No. 2017-008219, the contents of which are incorporated in the present specification. As a commercial item of a potential antioxidant, ADEKA ARKLSGPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and compounds represented by the formula (3 ) represented by the compound.

【Chemical formula 65】

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R ⁶ represents an extension of carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group which the resin has. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

Since it can act on a resin and a metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. A group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., may further have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.

The compounds represented by the general formula (3) include the following as examples, but are not limited to the following structures.

[Chemical formula 66]

[Chemical formula 67]

【Chemical formula 68】

【Chemical formula 69】

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the resin composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

[Anti-agglomeration agent] The resin composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

In this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01% by mass or more and 10% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

[Phenolic compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the product name above, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain the phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

[Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds, but when included, the content of the other polymer compounds is 0.01% by mass relative to the total solid mass of the composition of the present invention More than 30 mass % is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferable, 2,000 mm ² /s to 10,000 mm ² /s is more preferable, and 2,500 mm ² /s to 8,000 mm ² /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. If it is 1,000 mm ² /s or more, it is easy to coat with a film thickness required as an insulating film for rewiring, for example, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface shape can be obtained.

<Restrictions on Substances Contained in Resin Compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will be improved. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container at the time of storage, and the like are exemplified.

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm good. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

Further, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, there can be mentioned a method of selecting a raw material with a small metal content as a raw material constituting the resin composition of the present invention; The raw material of the product is filtered through a filter; the polytetrafluoroethylene and the like are lined in the device to conduct distillation under the condition that the pollution is suppressed as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm good. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably used.

As the storage container of the resin composition of the present invention, a conventionally known storage container can be used. Further, as the container, in order to suppress contamination of impurities into the raw material or the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is constituted by 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The cured product of the resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The hardening of the resin composition is preferably carried out by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C Excellent inside. The form of the cured product of the resin composition is not particularly limited, and a film form, a rod form, a spherical form, a granular form, and the like can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the curing can also be selected for the purposes of forming a protective film on the wall surface, forming a Beer hall for conduction, adjusting impedance, capacitance, internal stress, and imparting a heat release function. shape of things. The film thickness of the cured product (including the film of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%]=100-(volume after hardening÷volume before hardening)×100

<Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it may become a cured product excellent in mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

<Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. The mixing can employ mixing based on a stirring blade, mixing based on a ball mill, mixing by rotating the tank itself, and the like. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

In addition, in order to remove foreign matter, such as dust and fine particles, in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the filter material is polyethylene, HDPE (high density polyethylene) is better. Filters can be used pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm is connected in series as a first stage, and an HDPE filter having a pore diameter of 0.2 μm is connected in series as a second stage. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of pressurization and filtration, the pressure for pressurization is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and 0.05 MPa or more and 0.7 MPa or less. More preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine 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 mentioned. In addition, the step of degassing the resin composition filled in the bottle under reduced pressure after filtration using a filter may be implemented.

(Manufacturing method of hardened product) It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material. Moreover, the manufacturing method of the cured product of the present invention includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a developing step of developing the film exposed by the exposure step using a developer to form a pattern as follows: better. The method for producing a cured product of the present invention includes at least one of the above-mentioned film forming step, the above-mentioned exposure step, the above-mentioned developing step, and a heating step of heating the pattern obtained by the developing step, and a post-development exposure step of exposing the pattern obtained by the developing step. One is the best. Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation step and the step of heating the said film. Hereinafter, the details of each step will be described.

<Film formation step> The resin composition of the present invention can be used in a film forming step suitable for forming a film on a substrate. It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material.

[Substrate] The type of the substrate can be appropriately set according to the application, but it is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

Moreover, when forming a film by applying a resin composition to the surface of a resin layer (for example, the layer containing a hardened|cured material) or the surface of a metal layer, a resin layer or a metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferable.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray method or inkjet method are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and The slit coating method is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration or coating conditions of the resin composition according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP 2006-023696 A, or paragraphs 0096 to 0108 of JP 2006-047592 A can be preferably used in the present invention. . Also, a step of removing excess film in the end portion of the base material may be performed. Examples of such a step include edge bead rinse (EBR), back rinse, and the like. In addition, a pre-wetting step may be employed, in which the resin composition is applied after various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate.

<Drying step> After the film forming step (layer forming step), the above-mentioned film may be applied to the step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and further preferably 90-110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The above-mentioned film may be provided in the exposure step of selectively exposing the film. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process which selectively exposes the film formed by the film formation process. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, the exposed area (exposed part) and the unexposed area (non-exposed part) are formed on the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, the exposure energy at a wavelength of 365 nm is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² for better.

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

Regarding the exposure wavelength, if the relationship with the light source is described, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) ) High pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and the third harmonic is 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the film including the resin composition of the present invention, and exposure using a mask, exposure by direct laser imaging, etc. .

<Heating step after exposure> The above-mentioned film may be provided in a step of heating after exposure (post-exposure heating step). That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

<Development step> The above-mentioned film after exposure can be provided in the developing step of forming a pattern by developing with a developing solution. That is, the manufacturing method of the hardened|cured material of this invention may include the developing process which develops the film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of an exposed part and a non-exposed part of a film is removed, and a pattern is formed. Among them, the development of removing the non-exposed portion of the film by the development step is called negative development, and the development of removing the exposed portion of the film by the development step is called positive development.

[Developer] As the developing solution used in the image development step, a developing solution containing an alkaline aqueous solution or an organic solvent is exemplified.

When the developing solution is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH (hydroxide Tetramethylammonium), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, Methyldiethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydroxide Tetraoctylammonium, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2) hydroxide -Hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass in the total mass of the developer. good.

When the developing solution contains an organic solvent, the organic solvent as esters can preferably include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably cited Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, 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 cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, Preferred examples of alcohols include dimethyl sulfoxide, and preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, a developer especially comprising at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone More preferably, the developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferable, and the developer containing cyclopentanone is the most preferable.

When the developing solution contains an organic solvent, the content of the organic solvent relative to the total mass of the developing solution is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more The above are excellent. Moreover, the said content may be 100 mass %.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply developer] The method for supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle In order to carry out spin-on immersion development or continuous supply of developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate. The step of liquid solution can also be repeated several times. In addition, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can be preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.

[Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).

As the organic solvent when the rinse liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably cited Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, 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 cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, Preferred examples of alcohols include dimethyl sulfoxide, and preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid 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. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

The rinse solution may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through a liquid pan, and a method of showering A method of supplying a rinsing liquid to the substrate in the form of a method of continuously supplying the rinsing liquid to the substrate through a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

<Heating step> The pattern obtained by the developing step (the rinsed pattern in the case of performing the rinsing step) may be supplied to the heating step of heating the pattern obtained by the above-described development. That is, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by the developing process. Moreover, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by another method or the film obtained by the film formation process in the state which does not carry out the developing process. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. Moreover, the crosslinking etc. of the unreacted crosslinkable group in a specific resin or a crosslinking agent other than a specific resin are also performed. As the heating temperature (maximum heating temperature) in the heating step, 50-450°C is preferable, 150-350°C is more preferable, 150-250°C is further preferable, 160-250°C is further preferable, 160- 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and utilizing the action of a base generated from the base generator or the like.

The heating in the heating step is preferably performed at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The above-mentioned temperature increase rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature increase rate to 1°C/min or more, productivity can be ensured and excessive volatilization of the acid or solvent can be prevented, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured product can be relieved. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out a heating rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, from the temperature at the start of heating to the maximum heating temperature. 3 to 6°C/sec is more preferable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is, for example, higher than the temperature of the solvent contained in the resin composition of the present invention. It is preferable to start the temperature rise at a temperature that is 30 to 200°C lower in the boiling point.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and particularly 120°C or higher. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. As an example, the following steps may be performed: ramp from 25°C to 120°C at 3°C/min and hold at 120°C for 60 minutes, and ramp from 120°C to 180°C at 2°C/min and hold at 180°C for 120 minutes . Moreover, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the properties of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be two or more steps. For example, the pretreatment step of the first stage may be performed in the range of 100 to 150°C, and then the pretreatment step of the second stage 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.

From the viewpoint of preventing decomposition of the specific resin, the heating step is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. Although it does not specifically limit as a heating means in a heating process, For example, a hotplate, an infrared furnace, an electric oven, a hot-air oven, an infrared oven, etc. are mentioned.

<Exposure step after development> The pattern obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used in the development of the pattern after the exposure and development step in place of or in addition to the above-mentioned heating step. in the post-exposure step. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The manufacturing method of the cured product of the present invention may include a heating step and an exposure step after development, or may include only one of a heating step and an exposure step after development. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator can be accelerated, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step> The pattern obtained by the developing step (preferably the pattern provided to at least one of the heating step and the post-exposure developing step) can be provided in the metal layer forming step of forming the metal layer on the pattern. That is, it is preferable that the manufacturing method of the cured product of the present invention includes a metal layer forming step in which the pattern obtained by the developing step is provided to at least one of the heating step and the post-development exposure step. pattern is preferably formed on the metal layer.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, alloys containing these metals, copper and aluminum. More preferred, copper is further preferred.

The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are exemplified. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution is mentioned.

The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, in the thickest part.

＜Use＞ Examples of fields to which the cured product of the present invention can be produced or the cured product of the present invention include insulating films for electronic components, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting purposes as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

In addition, the manufacturing method of the cured product of the present invention or the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates or screen plates, the use of etching forming components, and the protection of protective varnishes and dielectric layers in electronics, especially microelectronics. manufacturing etc.

(Laminated body and method for producing the laminated body) The laminate system of the present invention refers to a structure having a plurality of layers including the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers including a cured product, and may be a layered body formed by layering three or more layers. At least one of the two or more layers including the cured product included in the laminate is a layer including the cured product of the present invention, from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the shrinkage, etc. It is also preferable that all the layers including the cured product included in the above-mentioned laminate are layers including the cured product of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include the process of repeating the manufacturing method of the hardened|cured material of this invention several times.

The layered product of the present invention includes two or more layers including a cured product, and an aspect including a metal layer between any of the above-mentioned layers including the cured product is preferred. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer including the cured product during the manufacturing method of the cured product performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layered structure in which at least three layers of a first layer including a cured product, a metal layer, and a second layer including a cured product are stacked in this order is preferably used. Preferably, the first layer including the cured product and the second layer including the cured product are both layers including the cured product of the present invention. The resin composition of the present invention for forming the first layer including the cured film and the resin composition of the present invention for forming the second layer including the cured film may be the same composition or may be make up different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

<Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process. The lamination step includes again sequentially performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, on the surface of the pattern (resin layer) or metal layer. A series of steps of at least one of the post-development exposure steps. However, at least one of the (a) film formation step and (d) the heating step and the post-development exposure step may be repeated. Moreover, the (e) metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.

When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after the metal layer is provided. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step is sequentially repeated (e) metal layer formation. The aspect of the step is the aspect of repeating in sequence (a) the film forming step, (d) the heating step, and the post-development exposure step, and (e) the metal layer forming step. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step.

(Surface activation treatment step) It is preferable that the manufacturing method of the layered product of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer forming step, but the resin composition layer may be surface activated after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step). After the processing step, a metal layer forming step is performed. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed resin composition layer, or may be performed on both the metal layer and the exposed resin composition layer, respectively. at least in part. Surface activation treatment is preferably performed on at least a part of the metal layer, and surface activation treatment is preferably performed on a part or all of a region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. Moreover, it is preferable to also perform surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activated by the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as in the case of performing negative development, it is difficult to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, Etching treatment of CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in Dipping treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma treatment using oxygen as a raw material gas is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , and most preferably 10,000-50,000 J/m ² .

(Manufacturing method of electronic components) Moreover, in this invention, the semiconductor element containing the hardened|cured material of this invention or the laminated body of this invention is also disclosed. Moreover, this invention also discloses the manufacturing method of the semiconductor element which includes the manufacturing method of the hardened|cured material of this invention or the manufacturing method of the laminated body of this invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used in the formation of the interlayer insulating film for rewiring layers, the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. These contents are incorporated into this specification. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

<Synthesis of Compound B-1> To a three-necked round-bottomed flask were added 23.73 g (0.150 mol) of diethylene glycol divinyl ether, 77.84 g (0.900 mol) of methacrylic acid, 100 ml of dry dichloromethane, and 39 mg of 4-Methoxyphenol was added with 125 mmg (0.54 mmol) of CSA (10-camphorsulfonic acid) while stirring at 20° C. or lower. It rose to about 40 degreeC temporarily, but fell immediately, and it stirred at 25 degreeC for 4 hours. After the completion of the reaction, the reaction solution was poured into a mixed solution of 500 ml of water containing 60 g of sodium bicarbonate and 300 ml of ethyl acetate, and the mixture was stirred for 30 minutes. The organic phase was separated, washed twice with 300 ml of saturated aqueous sodium bicarbonate solution, and once with 200 ml of saturated brine. After drying the organic phase with sodium sulfate, 25 mg of 4-methoxyphenol was added, and the mixture was concentrated under reduced pressure to obtain 46.31 g of an oily substance of B-1, the target product, in a yield of 93.4%. The H ¹ -NMR measurement results of Compound B-1 are as follows. 6.16(2H), 6.01(2H), 5.60(2H), 3.81(2H), 3.71(2H), 3.65(4H), 1.95(6H), 1.46(6H) [Chemical formula 70]

<Synthesis of Compound B-2> The following compound B-2 was synthesized with reference to the method described in Japanese Patent Laid-Open No. 2010-224558. 【Chemical formula 71】

<Synthesis of Compound B-3> Referring to the method described in JP-A-2014-169384, the following compound B-3 was synthesized. 【Chemical formula 72】

<Synthesis of Compound B-4> The following compound B-4 was synthesized with reference to the method described in Japanese Patent Laid-Open No. 2005-232412. 【Chemical formula 73】

<Synthesis of Compound B-5> In the synthesis of Compound B-1, except that methacrylic acid was changed to the following Compound B-5a in an equimolar amount, by the same method as Compound B-1, The following compound B-5 was synthesized. 【Chemical formula 74】

<Synthesis Example 1> [Synthesis of a polyimide precursor (A-1: Polyimide having no radical polymerizable group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol imide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N- In methylpyrrolidone, it was dried with molecular sieves. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C and it was added dropwise to the reaction mixture over 20 minutes. Next, after allowing the reaction mixture to react at 0°C for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature for 1 night. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000. 【Chemical formula 75】

<Synthesis Example 2> [Synthesis of a polyimide precursor (A-2: having radicals) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate Polyimide precursor for polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of methyl 2-hydroxyethyl acrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme (diglyme) were stirred at 60°C for 18 hours , produced a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , 4,4'-diaminodiphenyl ether was converted into a polyimide precursor by the same method as in Synthesis Example 1, and the A polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. 【Chemical formula 76】

<Synthesis Example 3> [Synthesis of a polyimide precursor (from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate) A-3: Polyimide precursor having a radically polymerizable group)] Mix 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hour), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme at 60°C It stirred at temperature for 18 hours, and produced the diester of 4,4'- oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , 4,4'-diaminodiphenyl ether was converted into a polyimide precursor by the same method as in Synthesis Example 1, and the A polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical formula 77]

<Synthesis Example 4> [From 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (bi-o-toluidine) and methacrylic acid 2-Hydroxyethyl ester to synthesize polyimide precursor (A-4: Polyimide precursor having a radically polymerizable group)] Mix 20.0 g (64.5 mmol) of 4,4'-oxybis Phthalic anhydride (dried at 140°C for 12 hours), 16.8g (129 mmol) 2-hydroxyethyl methacrylate, 0.05g hydroquinone, 20.4g (258 mmol) pyridine and 100 g of diglyme were stirred at a temperature of 60° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , by the same method as in Synthesis Example 1, 4,4'-diamino-2,2'-dimethylbiphenyl was converted into polyamide As an amine precursor, a polyimide precursor was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. 【Chemical formula 78】

<Synthesis Example 5> [Synthesis of a polybenzoxazole precursor from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzyl chloride ( A-5)] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone, and the mixture was stirred and allowed to dissolve. Next, 11.21 g of 4,4'-oxydibenzyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor was 15,000. 【Chemical formula 79】

<Synthesis example 6> [Synthesis of polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-6: Polyimide precursors with radically polymerizable groups)] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added to a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ- Butyrolactone. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exotherm due to the reaction was completed, it was left to cool to room temperature, and further left to stand for 16 hours.

Next, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. Next, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added while stirring for 60 minutes. Further, after stirring at room temperature for 2 hours, 30 ml of ethanol was added and the mixture was stirred for 1 hour. After that, 400 ml of gamma-butyrolactone was added. A reaction liquid was obtained by removing the precipitate formed in the reaction mixture by filtration.

The obtained reaction solution was added to 3 liters of ethanol to form a precipitate consisting of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum-dried, whereby a powdery polymer A-6 was obtained. The weight average molecular weight (Mw) of this polymer A-6 was measured to be 20,000.

<Synthesis Example 7> [Synthesis of polyimide precursor (A -7: Polyimide precursor having a radically polymerizable group)] In Synthesis Example 7, 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. The reaction was carried out in the same manner as the method described in Synthesis Example 6, whereby a polymer A-7 was obtained. The weight average molecular weight (Mw) of this polymer A-7 was measured to be 22,000.

<Examples and Comparative Examples> In each Example, each resin composition was obtained by mixing the components described in the following table, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components described in the following table, respectively. Specifically, let the content of the components described in the column other than "solvent" in the table be the amount described in the "parts by mass" of the table, and let the content of the components described in the column of "solvent" in the table be the amount described in the table. It is an amount such that the solid content concentration of the composition becomes the value described in the table. Also, for example, the descriptions of "I-1/I-2" and "80/20" in "Solvent" in the table indicate that the content ratio of I-1 and I-2 is, in mass ratio, I-1:I-2= 80:20. The obtained resin composition and the composition for comparison were subjected to pressure filtration through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in the table|surface, the description of "-" shows that a composition does not contain the corresponding component.

【Table 1】 Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Precursors of Cyclized Resins type A-3 A-3 A-3 A-3 A-3 A-3 A-1 A-2 A-4 A-5 A-3 A-3 A-3 A-3 parts by mass 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 Compound A type B-1 B-2 B-3 B-4 B-5 B-6 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 polymeric compound type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - polymerization initiator type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-1 D-1 D-1 parts by mass 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 alkali generator type E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-2 E-1 E-1 parts by mass 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 polymerization inhibitor type F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-2 F-1 parts by mass 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 migration inhibitor type G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-2 parts by mass 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 Metal Adhesion Improver type H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 parts by mass 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 solvent type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 parts by mass 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 additive type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - Evaluation results drug resistance A A A A A A B B B B A A A A Elongation at break A A A A A A A A A A A A A A

【Table 2】 Example Comparative example 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 1 2 3 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 40 40 40 40 Precursors of Cyclized Resins type A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-6 /A-7 A-6 /A-7 A-6 /A-7 A-6 /A-7 parts by mass 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 40/40 40/40 40/40 40/40 Compound A type B-1 B-1 B-3 B-3 B-3 B-3 B-3 B-1 B-1 B-1 B-1 - - - parts by mass 12.12 12.12 12.12 12.12 12.12 12.12 12.12 6.06 6.06 6.06 3.75 - - - polymeric compound type - - - - - - - C-1 C-1 C-1 C-1 C-1 C-1 C-2 parts by mass - - - - - - - 6.06 6.06 6.06 3 7.8 7.8 7.8 polymerization initiator type D-1 D-1 D-2 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 3.1 3.1 3.1 3.1 alkali generator type E-1 E-1 E-2 E-1 E-1 E-1 E-1 E-1 E-2 - - - - parts by mass 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 - - - - polymerization inhibitor type F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 F-1 F-1 F-3 F-3 F-3 F-3 parts by mass 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.05 0.05 0.05 0.05 migration inhibitor type G-1 G-1 G-1 G-1 G-1 G-2 G-1 G-1 G-1 G-1 G-2 /G-3 G-2 /G-3 G-2 /G-3 G-2 /G-3 parts by mass 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.15 /0.15 0.15 /0.15 0.15 /0.15 0.15 /0.15 Metal Adhesion Improver type H-2 H-1 H-1 H-1 H-1 H-1 H-2 H-1 H-1 H-1 H-2 H-2 H-2 H-2 parts by mass 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 0.5 0.5 0.5 0.5 solvent type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-3 I-3 I-3 I-3 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-2 /I-4 /I-4 /I-4 /I-4 parts by mass 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 additive type - - - - - - - - J-1 /J-2 J-1 /J-2 J-1 /J-2 - J-1 /J-2 J-1 /J-2 parts by mass - - - - - - - - 5.5/1 5.5/1 5.5/1 - 5.5/1 5.5/1 Evaluation results drug resistance A B A A A A A B B B B D D D Elongation at break A B A A A A A B B B C D D D

The details of each component described in the table are as follows.

[Cyclized resin or its precursor] ･A-1 to A-7: A-1 to A-7 synthesized in the above

[Compound A] ･B-1 to B-5: B-1 to B-5 synthesized above ･B-6: Compounds of the following structures [Chemical formula 80]

[Polymerizable compound] ･C-1: Compound of the following structure ･C-2: M-327 (caprolactone 3 of ethylene oxide modified triacrylate manufactured by TOAGOSEI CO., LTD. Molar modified product [Chemical formula 81]

[Additive] ･J-1: N-phenyldiethanolamine ･J-2: Compound of the following structure [Chemical formula 82]

[Photopolymerization initiator] ･D-1 and D-2: Compounds of the following structures [Chemical formula 83]

[Alkali generator] ･E-1 to E-2: Compounds of the following structures [Chemical formula 84]

[Polymerization inhibitor] ･F-1 to F-3: Compounds of the following structures ･F-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical formula 85]

[Migration inhibitor] G-1 to G-3: Compounds of the following structures. 【Chemical formula 86】

[Metal Adhesion Improver] ･H-1 to H-3: Compounds of the following structures [Chemical Formula 87]

[Solvent] I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethyl methylene (manufactured by FUJIFILM Wako Pure Chemical Corporation) I-3: N-methyl-2-pyrrolidone (manufactured by Ashland) I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation> [Manufacture of Cured Product] In each of the Examples and Comparative Examples, the resin composition or the comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer on which the resin layer was formed was dried on a hot plate at 100° C. for 4 minutes to form a resin composition layer having a uniform thickness of 20 μm on the silicon wafer. Using a broadband exposure machine (UX-1000SN-EH01, manufactured by USHIO INC.), the resin composition layer on the silicon wafer was exposed at an exposure energy of 400 mJ/cm ² , and the temperature was increased at a temperature increase rate of 5°C/min in a nitrogen atmosphere. After the exposed resin composition layer reached 180°C, it was heated at that temperature for 2 hours. The heated resin composition layer and the silicon wafer were immersed in a 3 mass % hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The above-mentioned peeled and heated resin composition layer was used as a cured product.

[Chemical resistance] The obtained cured product was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass % aqueous tetramethylammonium hydroxide (TMAH) solution Evaluation conditions: The cured product was immersed in the chemical solution at 75° C. for 15 minutes, the film thicknesses before and after the immersion were compared, and the dissolution rate (nm/min) was calculated. When measuring the film thickness, the film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22, manufactured by Foothill), and the average value was used as an arithmetic average to obtain the film thickness. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "chemical resistance" in the table. The smaller the value of the dissolution rate, the more excellent the chemical resistance of the cured product. -evaluation standard- A: The dissolution rate is less than 200 nm/min. B: The dissolution rate is 200 nm/min or more and less than 350 nm/min. C: The dissolution rate is 350 nm/min or more and less than 500 nm/min. D: The dissolution rate is 500 nm/min or more.

[Elongation at Break] In each of the Examples and Comparative Examples, the resin composition or the composition for comparison was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a uniform resin composition layer with a thickness of about 15 μm was obtained on the silicon wafer. The entire surface of the obtained resin composition layer was exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The resin composition layer (resin layer) after the exposure was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., it was heated for 3 hours. The cured resin layer (cured product) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched using a punching machine, and a test piece having a sample width of 3 mm and a sample length of 30 mm was produced. The obtained test piece was measured for fracture in the longitudinal direction of the film in accordance with JIS-K6251 at a crosshead speed of 300 mm/min in an environment of 25°C and 65% RH (relative humidity) using a tensile tester (TENSILON). Elongation. The evaluation was carried out five times each, and the arithmetic mean value of the elongation at the time of breaking of the film (elongation at break) was used as an index value. The above-mentioned index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break" in the table. It can be said that the larger the above-mentioned index value, the more excellent the film strength (elongation at break) of the obtained cured product. -Evaluation Criteria- A: The above-mentioned index value is 60% or more. B: The above-mentioned index value is 55% or more and less than 60%. C: The above-mentioned index value is 50% or more and less than 55%. D: The above index value is less than 50%.

From the above results, the obtained cured product of the resin composition containing the resin and the compound A of the present invention was found to be excellent in film strength. The compositions of Comparative Examples 1 to 2 did not contain Compound A. It turns out that the film strength of the obtained hardened|cured material of the composition of this comparative example 1-2 is inferior. Moreover, from the above-mentioned result, it turns out that the obtained hardened|cured material of the resin composition containing the resin and compound A of this invention is excellent in chemical resistance. The resin compositions of Comparative Examples 1 to 2 did not contain Compound A. It turns out that the adhesiveness of the hardened|cured material obtained by the resin composition of this comparative example 1-2 is inferior.

<Example 101> The resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate having the copper thin layer formed thereon in a layer by spin coating, and dried at 100° C. for 4 minutes On the other hand, after forming a photosensitive film having a film thickness of 20 μm, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line-to-space and a line width of 10 μm). After exposure, it was heated at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds, thereby obtaining a layer pattern. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.

Claims (21)

A resin composition comprising: Compound A, which has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure and has a molecular weight of less than 1000; and Precursors for cyclized resins. The resin composition according to claim 1, wherein The polymerizable group in the aforementioned compound A is a group having an ethylenically unsaturated bond. The resin composition according to claim 1 or claim 2, wherein The linking group in the aforementioned compound A contains a plurality of at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure. The resin composition according to claim 1 or claim 2, wherein The linking group in the aforementioned compound A contains plural cyclohexene structures or plural acetal structures. The resin composition according to claim 1 or claim 2, wherein the aforementioned compound A comprises a compound represented by the following formula (2-1), [Chemical formula 1]

In formula (2-1), R ¹ , R ² and R ³ each independently represent a monovalent organic group, and at least one of R ¹ , R ² and R ³ contains a group having a polymerizable group. The resin composition according to claim 5, wherein R ² and R ³ are groups having a partial structure represented by either the following formula (2-2) or the following formula (2-3), [Chemical formula 2]

In formula (2-2) and formula (2-3), R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bond with an oxygen atom contained in formula (2-1) At the junction site, L represents a divalent linker. The resin composition according to claim 5, wherein the compound represented by the aforementioned formula (2-1) is a compound represented by the following formula (2-4), [Chemical formula 3]

In formula (2-4), R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group. The resin composition according to claim 1 or claim 2, wherein The linking group in the aforementioned compound A contains a cyclohexene structure having a cross-linked ring structure or a condensed ring structure. The resin composition according to claim 1 or claim 2, wherein the aforementioned compound A comprises a compound represented by the following formula (3-1), [Chemical formula 4]

In formula (3-1), R ¹ and R ² each independently represent a monovalent organic group, and at least one of R ¹ and R ² contains a group having an ethylenically unsaturated bond. The resin composition according to claim 9, wherein the compound represented by the aforementioned formula (3-1) is a compound represented by the following formula (3-2), [Chemical formula 5]

In formula (3-2), R ³ and R ⁴ each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group. The resin composition according to claim 1 or claim 2, wherein The precursor of the aforementioned cyclized resin contains a polyimide precursor. The resin composition according to claim 11, wherein the aforementioned polyimide precursor has a repeating unit represented by the following formula (2), [Chemical formula 6]

In formula (2), 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 hydrogen Atom or a monovalent organic group. The resin composition according to claim 12, wherein at least one of R ¹¹³ and R ¹¹⁴ in the aforementioned formula (2) contains a radically polymerizable group. The resin composition according to claim 1 or claim 2, which further contains a radical polymerization initiator. The resin composition according to claim 1 or claim 2, which is used for forming an interlayer insulating film for a rewiring layer. A hardened product obtained by hardening the resin composition according to any one of claim 1 to claim 15. A layered body comprising two or more layers composed of the cured product according to claim 16, and including a metal layer between any of the cured product layers. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of Claims 1 to 15 on a substrate to form a film. The method for producing a cured product according to claim 18, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern. The manufacturing method of the hardened|cured material of Claim 18 which comprises the heating process of heating the said film at 50-450 degreeC. A semiconductor element containing the cured product of claim 16.