Resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device

Abstract

A resin composition which includes a resin that is either a cyclization resin or a precursor thereof, wherein said resin has a nitrogenous heteroring structure containing two or more nitrogen atoms as ring members and the proportion of the molar amount of a structure which includes the nitrogenous heteroring structure and leaves from said resin when said resin is heated at 1 atm and 350°C for 2 hours to the total molar amount of the nitrogenous heteroring structure contained in said resin is 10% or less; a cured object obtained by curing the resin composition; a layered product including the cured object; a method for producing the cured object; and a semiconductor device including the cured object or the layered product.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device. [Background technology]

[0002] Cyclic resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples in semiconductor devices for packaging include their use as insulating films, encapsulants, or protective films. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, cyclized resins such as polyimide are used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin. Such a resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The precursors of the cyclized resin, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product. Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, the industrial application development of the above-mentioned resin composition is increasingly expected from the standpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble resin and a photosensitive agent, characterized in that one end of the alkali-soluble resin is an organic group having an unsaturated group, and at least one of the side chain and the other end has a nitrogen-containing cyclic compound. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2008 / 059808 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In cured products containing cyclized resins such as polyimide, and components comprising a metal (e.g., a metal layer) in contact with the cured product (e.g., a device using the cured product as an insulating film), it is required that peeling between the metal and the cured product is less likely to occur even after a long period of time.

[0007] The present invention aims to provide a resin composition that yields a cured product that is less prone to peeling between the metal and the cured product even after a long period of time, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate. [Means for solving the problem]

[0008] Examples of typical embodiments of the present invention are shown below. <1> It contains a cyclized resin or a resin that is a precursor thereof, The above resin contains a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as ring members, The ratio of the molar amount of the nitrogen-containing heterocyclic structure that is detached from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin is 10% or less. Resin composition. <2> The above nitrogen-containing heterocyclic structure is present at the end of the above resin. <1> The resin composition described above. <3> The above resin includes a structure represented by the following formula (1-1) or formula (2-1): <1> or <2> The resin composition described above. [ka] In formula (1-1), L 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In formula (2-1), L 2 R is a linking group that does not contain a single bond or an oxazole ring structure, with an m+1 valent value. 2 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures. <4> It contains a cyclized resin or a resin that is a precursor thereof, The above resin includes a structure represented by the following formula (1-1) or formula (2-1). Resin composition. [ka] In formula (1-1), L 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In formula (2-1), L 2 R is a linking group that does not contain a single bond or an oxazole ring structure, with an m+1 valent value. 2 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures. <5> The composition contains 0.001 to 10% by mass of nitrogen-containing heterocyclic structures, each containing two or more nitrogen atoms as ring members, relative to the total solid content of the composition. <1> ~ <4> A resin composition as described in any one of the following. <6> The nitrogen-containing heterocyclic structure contained in the above resin includes an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton. <1> ~ <5> A resin composition as described in any one of the following. <7> The weight-average molecular weight of the above resin is between 1,500 and 70,000. <1> ~ <6> A resin composition as described in any one of the following. <8> Used for forming interlayer insulating films for redistribution layers, <1> ~ <7> A resin composition as described in any one of the following. <9> <1> ~ <8> A cured product obtained by curing the resin composition described in any one of the above. <10> <9> A laminate comprising two or more layers of the cured material described above, with a metal layer between any of the cured materials. <11> <1> ~ <8> A method for producing a cured product, comprising a film-forming step of applying a resin composition described in any one of the above to a substrate to form a film. <12> This includes an exposure step for exposing the above film to light and a developing step for developing the above film. <11> A method for producing the cured product described above. <13> The process includes a heating step of heating the above film to 50-450°C. <11> or <12> A method for producing the cured product described above. <14> <9> The cured product described above or <10> A semiconductor device including the laminate described above. [Effects of the Invention]

[0009] According to the present invention, a resin composition is provided that yields a cured product that is less likely to peel off between the metal and the cured product even after a long period of time; a cured product obtained by curing the resin composition; a laminate containing the cured product; a method for manufacturing the cured product; and a semiconductor device containing the cured product or the laminate. [Modes for carrying out the invention]

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, a numerical range represented by the symbol "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes insofar as they achieve their intended function. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "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, total solids refers to the total mass of all components of the composition excluding the solvent. In this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values, unless otherwise specified, and are measured using gel permeation chromatography (GPC). In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) may be used. Furthermore, unless otherwise specified, detection in GPC measurements will be performed using a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that the other layer is above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component. Furthermore, unless otherwise specified, the content of each component in a composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin composition) The resin composition according to the first aspect of the present invention contains a resin which is a cyclized resin or its precursor, the resin contains a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, and the resin contains the nitrogen-containing heterocyclic structure. The ratio of the molar amount of the structure containing the nitrogen-containing heterocyclic structure that desorbs from the resin when the resin is heated at 1 atm, 350 ° C for 2 hours to the total molar amount of the nitrogen-containing heterocyclic structure is 10% or less. The resin composition according to the second aspect of the present invention contains a resin which is a cyclized resin or its precursor, and the resin contains a structure represented by the following formula (1-1) or formula (2-1).

Chemical formula

[0012] Hereinafter, when simply described as "resin composition", it includes both the resin composition according to the first aspect of the present invention and the resin composition according to the second aspect. In addition, the resin which is the cyclized resin or its precursor according to the first aspect, or the resin corresponding to at least one of the cyclized resin or its precursor according to the second aspect is also referred to as "specific resin".

[0013] The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a film subjected to exposure and development using a developer solution containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is more preferably used to form interlayer insulating films for redistribution layers. Furthermore, the resin composition of the present invention may be used to form a photosensitive film for positive-type development, or for forming a photosensitive film for negative-type development. In the present invention, negative development refers to development in which unexposed areas are removed by development, and positive development refers to development in which exposed areas are removed by development. As the above-mentioned exposure method, developer, and developing method, for example, the exposure method, developer, and developing method described in the exposure step, developing step, and developing steps described in the description of the manufacturing method of the cured product described later may be used.

[0014] According to the resin composition of the present invention, a cured product can be obtained that is less prone to peeling between the metal and the cured product, even after a long period of time. The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows.

[0015] Conventionally, nitrogen-containing cyclic compounds such as tetrazoles and aminotetrazoles have been used in cured products to improve adhesion to metals. However, there has still been room for improvement in terms of the adhesion strength between the metal and the cured product over long periods of time. As a result of diligent research, the present inventors have found that if a cyclized resin or a resin precursor thereof contains a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as ring members, and the molar amount of the nitrogen-containing heterocyclic structure that is released from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours is 10% or less, or if the cyclized resin or a resin precursor thereof contains a structure represented by formula (1-1) or formula (1-2), then peeling between the metal and the cured product is less likely to occur even after a long period of time. Although the mechanism by which the above effect is obtained is unknown, it is thought that the nitrogen-containing heterocyclic structure is included in the resin, and that this structure does not desorb upon heating, or that it is a structure represented by formula (1-1) or formula (1-2) which is resistant to decomposition by heat, so that the resulting cured product also contains a nitrogen-containing heterocyclic structure in the resin. Because this nitrogen-containing heterocyclic structure exhibits excellent adhesion to the substrate (especially metal substrates), it is presumed that the adhesion between the resin in the cured product and the substrate will be strong, resulting in excellent adhesion between the resulting cured product and the substrate. Furthermore, compared to the case where only the above-mentioned nitrogen-containing cyclic compounds are used as low-molecular-weight components, the present invention, which includes a nitrogen-containing heterocyclic structure in the resin, can reduce the amount of low-molecular-weight components in the composition, and therefore the resulting cured product is expected to have excellent chemical resistance. In addition, as mentioned above, since the amount of low-molecular-weight components in the composition can be reduced, it is presumed that the resulting cured product will also have excellent surface uniformity (i.e., surface smoothness) on the surface of the cured product.

[0016] Here, in the case of the resin described in Patent Document 1, which has a nitrogen-containing cyclic compound in at least one of the side chain and the other end, it is considered that the molar proportion of the structure containing the nitrogen-containing heterocyclic structure that is detached from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours is significantly more than 10%. When using such resins, it is likely that delamination will occur between the metal and the cured material after a long period of time.

[0017] The components included in the resin composition of the present invention will be described in detail below.

[0018] <Specific resin> A resin composition according to a first aspect of the present invention comprises a cyclized resin or a resin that is a precursor thereof (a specific resin), wherein the resin comprises a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, and the ratio of the molar amount of the nitrogen-containing heterocyclic structure that is removed from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin is 10% or less.

[0019] [Nitrogen-containing heterocyclic structure] The nitrogen-containing heterocyclic structure in the specified resin is a heterocyclic ring containing two or more nitrogen atoms as ring members. The nitrogen-containing heteroring structure may be monoring or polyring, preferably monoring or fused ring, more preferably 5-membered ring or 6-membered ring monoring, or fused ring of 5-membered rings, fused ring of 6-membered rings, or fused ring of a 5-membered ring and a 6-membered ring, and more preferably 5-membered ring monoring or fused ring of a 5-membered ring and a 6-membered ring. However, if the nitrogen-containing heterocyclic structure is a bicyclic structure, at least one monocyclic ring constituting the bicyclic ring contains two or more nitrogen atoms as ring members. That is, for example, a benzimidazole ring is considered a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members as defined in this invention, but a 7-azaindole ring is not considered a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members as defined in this invention. Furthermore, the above nitrogen-containing heterocyclic structure may have multiple nitrogen-containing heterocyclic structures within the bicyclic structure, each containing two or more nitrogen atoms as ring members, similar to the purine ring structure. The above nitrogen-containing heterocyclic structure may include heteroatoms other than nitrogen as ring members, but an embodiment in which the nitrogen-containing heterocyclic structure does not include heteroatoms other than nitrogen as ring members is also one of the preferred embodiments of the present invention. Examples of heteroatoms other than nitrogen include oxygen atoms and sulfur atoms. The above nitrogen-containing heterocyclic structure may be an aliphatic ring or an aromatic ring, but it is preferable that it be an aromatic ring.

[0020] From the viewpoint of adhesion strength after a long period of time, among these, the nitrogen-containing heterocycle preferably contains an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton, more preferably an imidazole ring, a triazole ring, a tetrazole ring, or a condensed ring of these rings with other rings, and even more preferably a benzimidazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, or a purine ring. Other rings mentioned above include aromatic rings, more preferably five-membered or six-membered aromatic rings, and even more preferably benzene rings.

[0021] The above nitrogen-containing heterocyclic structure is preferably located at the end of the specific resin, and more preferably at the end of the main chain of the specific resin. In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule. It is preferable that at least one of the main chain ends of the specific resin has the above-mentioned nitrogen-containing heterocyclic structure.

[0022] The specific resin in the resin composition according to the first aspect of the present invention preferably includes a structure represented by the following formula (1-1) or formula (2-1). The specific resin in the resin composition according to the second aspect of the present invention includes a structure represented by the following formula (1-1) or formula (2-1). In particular, when the specific resin is any of polyimide, polyimide precursor, polyamideimide, or polyamideimide precursor, it is preferable that it contains a structure represented by the following formula (1-1). Furthermore, if the specific resin is a polybenzoxazole or a polybenzoxazole precursor, it is preferable that it contains a structure represented by the following formula (2-1). [ka] In formula (1-1), L 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1* represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In formula (2-1), L 2 R is a linking group that does not contain a single bond or an oxazole ring structure, with an m+1 valent value. 2 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures.

[0023] In formula (1-1), L 1 This is a single bond, or an n+1 valent hydrocarbon group, or a hydrocarbon group with -O-, -C(=O)-, -NR inside. N It is preferable that the group contains at least one structure selected from the group consisting of -, -S-, and -S(=O)2-. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Also, L 1 An embodiment in which the bond is a single bond is also one of the preferred embodiments of the present invention.

[0024] In formula (1-1), R 1 The preferred embodiment is the same as the preferred embodiment of the nitrogen-containing heterocyclic structure described above.

[0025] In formula (1-1), n ​​is preferably an integer between 1 and 4, more preferably 1 or 2, and even more preferably 1.

[0026] In formula (1-1), * represents a bonding site with another structure. Here, one preferred embodiment of the present invention is one in which two *s are bonded to carbon atoms connected by covalent bonds to form an imide ring structure including the imide structure described in formula (1-1). As the above imide ring structure, a five-membered ring structure is preferred, for example.

[0027] In formula (2-1), L 2Preferably, the group is a single bond, an n+1 valent hydrocarbon group, or a hydrocarbon group containing at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, and -S(=O)2-. Also, L 2 An embodiment in which the bond is a single bond is also one of the preferred embodiments of the present invention.

[0028] In formula (2-1), R 2 The preferred embodiment is the same as the preferred embodiment of the nitrogen-containing heterocyclic structure described above.

[0029] In formula (2-1), m is preferably an integer between 1 and 4, more preferably 1 or 2, and even more preferably 1.

[0030] In formula (2-1), * represents a bonding site with another structure. Here, one preferred embodiment of the present invention is a configuration in which two *s are bonded to carbon atoms connected by covalent bonds, respectively, to form a ring structure containing nitrogen and oxygen atoms as described in formula (2-1). As the above ring structure, for example, an oxazole ring structure is preferred.

[0031] The specific resin preferably contains a structure that includes the structure represented by formula (1-1), and more preferably a structure that includes any of the following formulas (1-2) to (1-3). [ka] In equation (1-2) or equation (1-3), L 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In equation (1-2) or equation (1-3), L 1 , R 1 and n are L in equation (1-1), respectively. 1 , R 1 This is synonymous with n, and the preferred embodiment is similar.

[0032] Furthermore, the specific resin preferably includes a structure that contains the structure represented by formula (2-1), and more preferably a structure that contains any of the following formulas (2-2) to (2-3). [ka] In equation (2-2) or equation (2-3), L 2 R is a linking group that does not contain a single bond or an oxazole ring structure, with an m+1 valent value. 2 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures. In equation (2-2) or equation (2-3), L 2 , R 2 and m are L in equation (2-1), respectively. 2 , R 2 This is synonymous with m, and the preferred embodiment is also similar.

[0033] If the specific resin includes the structure represented by formula (1-1) above, it is also preferable that the specific resin includes the structure represented by formula (1-4) below. [ka] In formula (1-4), A 1 represents an oxygen atom or -NH-, R 115 represents a tetravalent organic group, R 114 L represents a hydrogen atom or a monovalent organic group. 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In formula (1-4), A 1 , R 115 and R 114 This is A in equation (2) described below. 1 , R 115 and R 114 This is synonymous with the same as the preferred configuration. In formula (1-4), L 1 , R1 And n is L in equation (1-1) above. 1 , R 1 This is synonymous with n, and the preferred embodiment is similar. Furthermore, if the specific resin contains a structure represented by formula (1-4), it is preferable that the specific resin contains a repeating unit represented by formula (2), which will be described later. If the specific resin contains repeating units represented by formula (2) described below, then A in formula (1-4) 1 , R 115 and R 114 A in any of the repeating units represented by formula (2) contained in the specific resin 1 , R 115 and R 114 It is also preferable that it has the same structure as [another entity]. Furthermore, if the specific resin contains repeating units represented by formula (2) described below, then * in formula (1-4) is equivalent to R in formula (2). 111 It is also preferable that it be a binding site with [another entity].

[0034] Furthermore, if the specific resin includes the structure represented by formula (1-1) above, it is also preferable that the specific resin includes the structure represented by formula (1-5) below. [ka] In formula (1-5), R 132 This represents a tetravalent organic group, L 1 R is a linking group that does not contain a single bond or an imide ring structure, with n+1 valent values. 1 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer greater than or equal to 1, and * represents a bonding site with other structures. In formula (1-5), R 132 This is R in equation (4) described later. 132 This is synonymous with the same as the preferred configuration. In formula (1-5), L 1 , R 1 And n is L in equation (1-1) above. 1 , R 1 This is synonymous with n, and the preferred embodiment is similar. Furthermore, if the specific resin contains a structure represented by formula (1-5), it is preferable that the specific resin contains a repeating unit represented by formula (4), which will be described later. If the specific resin contains repeating units represented by formula (4) described below, then R in formulas (1-5) 132 This refers to R in any of the repeating units represented by formula (4) contained in the specific resin. 132 It is also preferable that it has the same structure as [another entity]. Furthermore, if the specific resin contains repeating units represented by formula (4) described below, * in formulas (1-5) is equivalent to R in formula (4). 131 It is also preferable that it be a binding site with [another entity].

[0035] If the specific resin includes the structure represented by formula (2-1) above, it is also preferable that the specific resin includes the structure represented by formula (2-4) below. [ka] In formula (2-4), R 122 represents a tetravalent organic group, R 124 represents a hydrogen atom or a monovalent organic group, L 2 R is a linking group that does not contain a single bond or an oxazole ring structure, with an m+1 valent value. 2 * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures. In formula (2-4), R 122 and R 124 This is R in equation (3) described later. 122 and R 124 This is synonymous with the same as the preferred configuration. In formula (2-4), L 2 , R 2 And m is L in equation (2-1) above. 2 , R 2 This is synonymous with m, and the preferred embodiment is also similar. Furthermore, if the specific resin contains a structure represented by formula (2-4), it is preferable that the specific resin contains a repeating unit represented by formula (3) described later. When the specific resin contains a repeating unit represented by the following formula (3), R in formula (2-4) 122 and R 124 are preferably the same as R in any of the repeating units represented by formula (3) contained in the specific resin 122 and R 124 in structure. Also, when the specific resin contains a repeating unit represented by the following formula (3), * in formula (2-4) is preferably the bonding site with R 121 in formula (3).

[0036] When the specific resin contains the structure represented by the above formula (2-1), the specific resin preferably contains the structure represented by the following formula (2-5).

Chemical formula

[0037] The following are specific examples of structures containing nitrogen-containing heterocyclic structures with two or more nitrogen atoms as ring members, which are included in certain resins, but the present invention is not limited thereto. In the structures below, * indicates a bonding site with another structure. [ka]

[0038] The content of nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as ring members (also referred to as "content A") relative to the total solid content of the composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, and even more preferably 0.1 to 5% by mass. However, the above content A includes not only the content of the nitrogen-containing heterocyclic structure contained in the specific resin, but also the content of any other compounds having a nitrogen-containing heterocyclic structure (for example, the migration inhibitors described later) if such compounds are included. In other words, if the composition contains only a specific resin as a compound containing the above-mentioned nitrogen-containing heterocyclic structure, the content A is a value represented by the following formula. Content A = (Mass of specific resin × Molecular weight of the heterocycle contained in the specific resin / Molecular weight of the specific resin) / (Total solids) × 100 Furthermore, if the composition includes a specific resin and component 1 (for example, a migration inhibitor described later) as compounds containing the above nitrogen-containing heterocyclic structure, the content A is a value represented by the following formula. Content A = {(Mass of specific resin × Molecular weight of the heterocycle contained in the specific resin / Molecular weight of the specific resin) + (Mass of component 1 × Molecular weight of the heterocycle contained in component 1 / Molecular weight of component 1)} / (Total solids) × 100 Furthermore, the content of nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as ring members per mole of a specific resin is preferably 1 to 4 moles, and more preferably 1 to 2 moles.

[0039] [Percentage of molar amounts of the nitrogen-containing heterocyclic structure that is eliminated] Here, the molar proportion of the nitrogen-containing heterocyclic structure that is detached from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours can be determined as follows. One mole of resin is placed alone in a sealed container and heated at 350°C for 2 hours under 1 atmosphere of pressure. The amount of nitrogen-containing heterocyclic structures that have been removed is then quantified using HPLC (high-performance liquid chromatography). Then, the above percentage (%) is calculated according to the following formula. Percentage (%) = (Molar amount of the structure containing the detached nitrogen-containing heterocyclic structure) / (Molar amount of the above nitrogen-containing heterocyclic structure contained in the resin) The above percentage is 10% or less, preferably 8% or less, and more preferably 5% or less. Furthermore, the lower limit of the above percentage is not particularly limited and may be 0%.

[0040] The weight-average molecular weight of the specific resin is preferably 1,500 to 70,000, and more preferably 10,000 to 50,000.

[0041] The specified resin is a cyclized resin or its precursor. The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. In other words, the resin composition of the present invention preferably contains, as a specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition of the present invention. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. From such a resin composition of the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0042] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in type, but it is preferable that it contains repeating units represented by the following formula (2). [ka] In formula (2), A 1 and A 2 Each of these independently represents an oxygen atom or -NH-, and R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0043] A in equation (2) 1and A 2 Each of these independently represents either an oxygen atom or -NH-, with the oxygen atom being preferred. R in equation (2) 111 -Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of 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, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. The preferred ranges for these are as described above.

[0044] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine is preferably a diamine containing 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, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0045] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0046] Diamines include, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamines; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 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)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-Bis(4-aminophenyl)-10-Hydroanthracene, 3,3',4,4'-Tetraaminobiphenyl, 3,3',4,4'-Tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- 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-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0047] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0048] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0049] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0050] Also, R 111From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0051] R in equation (2) 115 represents a tetravalent organic group. Preferably, the tetravalent organic group is one containing an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents a bonding site with another structure. [ka] In formula (5), R 112 The linking group is a single bond or a divalent linking group, preferably a single bond or a group selected from a C1-C10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO2-, and -NHCO-, which may be substituted with a fluorine atom, and combinations thereof; more preferably a group selected from a single bond or a C1-C3 alkylene group, -O-, -CO-, -S-, and -SO2-, which may be substituted with a fluorine atom; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0052] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R 115 The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in equation (2) is 115 This is synonymous with the same thing, and the preferred range is also similar.

[0053] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-diphenylsulfide tetracarboxylic dianhydride, 3,3’,4,4’-diphenylsulfone tetracarboxylic 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-naphthalenetetracarboxylic dianhydride, 2,2’,3,3’-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0054] Also, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0055] In formula (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.

[0056] In formula (2), R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Also, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. As the radical polymerizable group of the polyimide precursor, a group having an ethylenic unsaturated bond is preferable. Examples of the group having an ethylenic unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (III), etc., and a group represented by the following formula (III) is preferable.

[0057]

Chemical formula

[0058] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferable. In formula (III), * represents the bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 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 polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the above-mentioned group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

[0059] In equation (2), R 113 If R is a hydrogen atom, 114 If the atom is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0060] In equation (2), R 113 and R 114 At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group are preferred.

[0061] Furthermore, it is preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0062] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0063] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to broaden the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, R 111 and R 112 Each of these independently represents a divalent organic group, R 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0064] A 1 , A 2 , R 111 , R 113 and R 114 These are, independently of A in equation (2), 1 , A 2 , R 111 , R113 and R 114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) 112 This is synonymous with the same thing, and the preferred range is also similar.

[0065] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0066] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0067] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 1,500 to 100,000, more preferably 1,500 to 70,000, even more preferably 5,000 to 70,000, particularly preferably 10,000 to 50,000, and most preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, even more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. The degree of molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains a plurality of polyimide precursors as specific resins, 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. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the plurality of polyimide precursors as one resin are each within the above ranges.

[0068] 〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23 °C in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium. From the viewpoint of pattern formation property, it is preferably a polyimide that dissolves 0.5 g or more, and more preferably a polyimide that dissolves 1.0 g or more. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less. Further, from the viewpoint of the film strength and insulation of the obtained organic film, the polyimide preferably has a plurality of imide structures in the main chain. In this specification, the "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to the other bond chains.

[0069] -Fluorine atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has a fluorine atom. The fluorine atom is, for example, R in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4) 131 and is preferably contained in R in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4) 131It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0070] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms. The silicon atom is preferably included in R131 in the repeating unit represented by formula (4) described later, and more preferably included in R131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later. Furthermore, the silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0071] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 131Preferably, it is included in the repeating unit R represented by formula (4) described later. 131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0072] [ka]

[0073] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0074] In formula (IV), R 21 This represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof. Of the alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0075] Among these, R 21 It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). 21 This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in L are as described above for R 21 This is similar to the preferred embodiment of the alkylene group having 2 to 12 carbon atoms, or the (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In equations (R1) to (R3), * is equivalent to * in equation (IV), and the same applies to the preferred embodiment. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0076] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0077] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0078] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds. Polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having an ethylenically unsaturated bond include, for example, R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0079] -Polar Conversion Group- Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. 131 , R 132 It is found at the ends of polyimides, etc.

[0080] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​shall be those calculated using ACD / ChemSketch®. Alternatively, values ​​published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to. Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. The polyimide preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0081] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0082] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, R 132 This represents a tetravalent organic group. If it has polymerizable groups, the polymerizable groups are R 131 and R 132 It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups are equivalent to formula (4). Formula (4-2) [ka] R 134 and R 135 At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0083] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. R 131 R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is 111 Similar examples are given, and the preferred range is also similar. Also, R 131Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. 111 Examples include:

[0084] R 131 It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine that does not contain an aromatic ring.

[0085] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0086] R 132 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is 115 Similar examples are given, and the preferred range is also similar. For example, R 115 The four bonds of the tetravalent organic group, as exemplified above, bond with the four -C(=O)- parts in formula (4) above to form a fused ring.

[0087] Also, R 132 Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor.115 Examples include: From the standpoint of the strength of the organic film, R 132 It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0088] R 131 and R 132 It is also preferable that at least one of them has an OH group. More specifically, R 131 As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R 132 As such, (DAA-1) to (DAA-5) above can be cited as more preferable examples.

[0089] Furthermore, it is preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

[0090] Furthermore, to improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0091] Furthermore, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-captives such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-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. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0092] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was found at 1377 cm⁻¹. -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0093] Polyimides are all of the same type R 131 or R 132 It may include the repeating unit represented by the above formula (4), and may include two or more different types of R 131 or R 132 The polyimide may also contain repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (2).

[0094] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0095] The weight-average molecular weight (Mw) of the polyimide is preferably 1,500 to 100,000, more preferably 1,500 to 70,000, even more preferably 5,000 to 70,000, particularly preferably 10,000 to 50,000, and most preferably 15,000 to 40,000. By setting the weight-average molecular weight to 1,500 or higher, the flexural resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyimide is preferably 1,000 to 40,000, more preferably 2,000 to 40,000, even more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. The degree of molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit set for the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[0096] [Polybenzoxazole precursor] The polybenzoxazole precursor used in this invention does not have any particular structure, but preferably contains repeating units represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0097] In equation (3), R 123 and R 124 These are R in equation (2), respectively. 113 This is synonymous with the same, and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group. In equation (3), R 121 R represents a divalent organic group. A divalent organic group is preferably one containing at least one of an aliphatic group and an aromatic group. A linear aliphatic group is preferred. 121 A dicarboxylic acid residue is preferred. One or more dicarboxylic acid residues may be used.

[0098] As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred. As for dicarboxylic acids containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, and dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. Examples include suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formula.

[0099] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0100] As for dicarboxylic acids containing aromatic groups, dicarboxylic acids having the following aromatic groups are preferred, and dicarboxylic acids consisting only of the following aromatic groups and two -COOH groups are more preferred.

[0101] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and * represents a binding site with another structure, independently.

[0102] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0103] In equation (3), R 122 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) above is 115 This is synonymous with the same thing, and the preferred range is also similar. R 122It is also preferable that the group is derived from a bisaminophenol derivative, and examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4-amino Examples include 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, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used individually or in combination.

[0104] Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

[0105] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent 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. Also, R 122 It is also preferable that the structure be represented by the above formula. 122However, if the structure is represented by the above formula, then of the four * and # characters, any two of them are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the other two are R in formula (3). 122 It is preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 Either the bond site with the nitrogen atom to which it is bonded, or the two *s are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the two #s are R in formula (3). 122 It is more preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 It is even more preferable that the site is a bonding site with the nitrogen atom to which it is bonded.

[0106] The bisaminophenol derivative is also preferably a compound represented by formula (As). [ka]

[0107] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0108] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

[0109] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferable because it further enhances the effect of high cyclization rate when cured at low temperatures.

[0110] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, as this maintains the effects of high transparency to i-lines and a high cyclization rate when cured at low temperatures.

[0111] Furthermore, it is even more preferable that R1 in the above formula (As) is an alkylene or a substituted alkylene. Specific examples of alkylenes and substituted alkylenes for R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable because they allow for the production of a well-balanced polybenzoxazole precursor that maintains high transparency to i-lines and a high cyclization rate when cured at low temperatures, while also having sufficient solubility in solvents.

[0112] For a method of producing the bisaminophenol derivative represented by the above formula (As), refer to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

[0113] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated herein by reference. Of course, it goes without saying that we are not limited to these.

[0114] The polybenzoxazole precursor may include other types of repeating units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that it can suppress the occurrence of warping associated with ring closure.

[0115] [ka] In equation (SL), Z has an a structure and a b structure, and R 1s R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 2s R is a hydrocarbon group having 1 to 10 carbon atoms. 3s , R 4s , R 5s , R 6s At least one of the groups is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of structures a and b may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol% for structure a, 95 to 5 mol% for structure b, and 100 mol% for a + b.

[0116] In formula (SL), preferred Z is R in the b structure. 5s and R 6s Examples include those in which the group is a phenyl group. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, thereby achieving both the effect of suppressing warping and the effect of improving solvent solubility.

[0117] When other types of repeating units include diamine residues represented by formula (SL), it is also preferable to include tetracarboxylic acid residues remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as repeating units. An example of such tetracarboxylic acid residues is R in formula (2). 115 Examples include:

[0118] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 1,500 to 70,000, more preferably 18,000 to 30,000, even more preferably 20,000 to 29,000, and particularly preferably 22,000 to 28,000. The number-average molecular weight (Mn) is preferably 1,000 to 14,000, more preferably 7,200 to 14,000, even more preferably 8,000 to 12,000, and particularly preferably 9,200 to 11,200. The degree of molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole precursor, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazole precursors are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polybenzoxazole precursors as a single resin are, respectively, within the above range.

[0119] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) that has a polymerizable group. A radical polymerizable group is preferred as the polymerizable group. Alternatively, it may be a compound represented by the following formula (X) that has a polarity conversion group such as an acid-degradable group. [ka] In formula (X), R 133represents a divalent organic group, R 134 This represents a tetravalent organic group. If it has a polarity-converting group such as a polymerizable group or an acid-degradable group, the polarity-converting group such as a polymerizable group or an acid-degradable group is R 133 and R 134 It may be located at least one of the two, or it may be located at the terminal end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below. Formula (X-1) [ka] In formula (X-1), R 135 and R 136 At least one of the groups is a polarity-converting group such as a polymerizable group or an acid-degradable group; if it is not a polarity-converting group such as a polymerizable group or an acid-degradable group, it is an organic group; and the other group is equivalent to formula (X). Formula (X-2) [ka] In formula (X-2), R 137 is a polarity-converting group such as a polymerizable group or an acid-degradable group, the others are substituents, and the other groups are synonymous with formula (X).

[0120] Polarity-converting groups such as polymerizable groups or acid-degradable groups are synonymous with the polymerizable groups described above in relation to the polymerizable groups of the polyimide precursor.

[0121] R 133 R represents a divalent organic group. Examples of divalent organic groups include aliphatic groups and aromatic groups. A specific example is R in formula (3) of the polybenzoxazole precursor. 121 Examples include R. 121 It is similar to that.

[0122] R 134 R represents a tetravalent organic group. An example of a tetravalent organic group is R in formula (3) of the polybenzoxazole precursor. 122 Examples include R. 122It is similar to that. For example, R 122 The four bonders of the tetravalent organic group, as exemplified above, bond with the nitrogen and oxygen atoms in formula (X) to form a fused ring. For example, R 134 However, if it is the following organic group, it forms the following structure. In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively. [ka]

[0123] The polybenzoxazole preferably has an oxazole conversion rate of 85% or more, and more preferably 90% or more. There is no particular upper limit, and it may be 100%. By having an oxazole conversion rate of 85% or more, the membrane shrinkage due to ring closure that occurs when oxazole is converted by heating is reduced, and the occurrence of warping can be suppressed more effectively. The above oxazole conversion rate can be measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm², which originates from the amide structure of the precursor, was observed. -1 Determine the peak intensity Q1 in the vicinity. Next, 1490 cm -1 The absorption intensity of aromatic rings found nearby is used for normalization. After heat treatment of the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the spectroscopy is performed at 1650 cm⁻¹. -1 The peak intensity Q2 in the vicinity was calculated to be 1490 cm. -1 The absorption intensity of the aromatic rings observed nearby is used for normalization. Using the normalized peak intensities Q1 and Q2 obtained, the oxazole rate of polybenzoxazole can be determined based on the following formula. Oxazole conversion rate (%) = (Specific value of peak intensity Q1 / Specific value of peak intensity Q2) × 100

[0124] Polybenzoxazoles are all of the same type as R 131 or R 132 The above formula (X) may include a repeating unit containing two or more different types of R 131 or R132 The polybenzoxazole may contain repeating units of the above formula (X), including the above formula (X). In addition, the polybenzoxazole may contain other types of repeating units besides the repeating units of the above formula (X).

[0125] Polybenzoxazoles are, for example, bisaminophenol derivatives and R 133 It is obtained by reacting a dicarboxylic acid containing or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, and then oxazoleizing this using a known oxazole reaction method. In the case of dicarboxylic acids, to increase the reaction yield, etc., an activated ester-type dicarboxylic acid derivative that has been pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.

[0126] The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 1,500 to 70,000, more preferably 5,000 to 70,000, even more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight-average molecular weight to 1,500 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more types of polybenzoxazole are contained, it is preferable that the weight-average molecular weight of at least one of the polybenzoxazoles is within the above range. Furthermore, the number-average molecular weight (Mn) of polybenzoxazole is preferably 1,000 to 14,000, more preferably 7,200 to 14,000, even more preferably 8,000 to 12,000, and particularly preferably 9,200 to 11,200. The degree of molecular weight dispersion of the polybenzoxazole is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazoles are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polybenzoxazole are treated as a single resin are, respectively, within the above range.

[0127] [Polyamide-imide precursors] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2). [ka] 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-, R 113 represents a hydrogen atom or a monovalent organic group.

[0128] In formula (PAI-2), R 117 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0129] Also, R 117 It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the above tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used individually or in combination of two or more.

[0130] Specifically, preferred tricarboxylic acid compounds include 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 having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0131] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene group. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

[0132] In formula (PAI-2), R 111 , A 2 , R 113 These are the R values ​​in equation (2) above. 111 , A 2 , R 113 This is synonymous with the same as the preferred configuration.

[0133] The polyamide-imide precursor may further contain other repeating units. Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below. [ka]

[0134] In formula (PAI-1), R 116 represents a divalent organic group, R 111 This represents a divalent organic group. In formula (PAI-1), R 116 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0135] Also, R 116 It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

[0136] Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include 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 having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0137] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebaic acid, and hexadeca. Examples include fluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

[0138] In formula (PAI-1), R 111 R in equation (2) above is 111 This is synonymous with the same as the preferred configuration.

[0139] Furthermore, the polyamide-imide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0140] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine component.

[0141] One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2). The polyamide-imide precursor may contain all of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2); it may contain the repeating units represented by formula (PAI-2) and formula (PAI-1) but not the repeating units represented by formula (2); it may contain the repeating units represented by formula (PAI-2) and formula (2) but not the repeating units represented by formula (PAI-1); or it may contain the repeating units represented by formula (PAI-2) but not the repeating units represented by formula (PAI-1) and formula (2). Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0142] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 1,500 to 500,000, more preferably 1,500 to 100,000, even more preferably 1,500 to 70,000, particularly preferably 5,000 to 70,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyamide-imide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyamide-imide precursors as a single resin are, respectively, within the above ranges.

[0143] [Polyamide-imide] The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide, or a polyamide-imide that is soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyamide-imide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in its main chain.

[0144] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamide-imide contains fluorine atoms. Fluorine atoms, for example, are R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0145] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamide-imide may have ethylenically unsaturated bonds. Polyamide-imides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as a group having an ethylenically unsaturated bond. A preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

[0146] The amount of ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0147] -Polymerizable groups other than ethylenically unsaturated bonds- Polyamide-imides may have polymerizable groups other than ethylenically unsaturated bonds. Polymerizable groups other than ethylenically unsaturated bonds in polyamide-imides include the same groups as those described above for polymerizable groups other than ethylenically unsaturated bonds in polyimides. Polymerizable groups other than ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (PAI-3) described later. 111 It is preferable that it be included in The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0148] -Polar Conversion Group- Polyamide-imides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyamide-imides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same.

[0149] - Acid Value - When polyamide-imide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamide-imide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyamide-imide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, examples of acid groups contained in polyamideimides include the same groups as those in the polyimides described above, and the preferred embodiments are also the same.

[0150] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyamide-imide has a phenolic hydroxyl group. Polyamide-imides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. Phenolic hydroxyl groups are, for example, R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0151] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 These are the R values ​​in equation (PAI-2), respectively. 111 and R 117 This is synonymous with the same as the preferred configuration. If it has polymerizable groups, the polymerizable groups are R 111 and R 117 It may be located at least one of the two or at the end of the polyamide-imide.

[0152] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to encapsulate the main chain ends of the polyamide-imide with an end-capturing agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. The preferred embodiment of the end-capturing agent is the same as the preferred embodiment of the end-capturing agent in polyimide described above.

[0153] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of polyamide-imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

[0154] Polyamide-imides are all of the same type R 111 or R 117 It may include the repeating unit represented by the above formula (PAI-3), and may contain two or more different types of R 131 or R 132The polyamide-imide may also contain repeating units represented by the above formula (PAI-3). In addition to the repeating units represented by the above formula (PAI-3), the polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0155] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and then completely imidizing it using a known imidation reaction method, or by stopping the imidation reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with its polyamide-imide precursor to introduce a partial imide structure.

[0156] The weight-average molecular weight (Mw) of the polyamide-imide is preferably 1,500 to 70,000, more preferably 5,000 to 70,000, even more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight-average molecular weight to 1,500 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of molecular weight dispersion of the polyamide-imide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of molecular weight dispersion of the polyamide-imide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imides are treated as a single resin are, respectively, within the above ranges.

[0157] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, 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 materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0158] -End-capturing agent- To introduce a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members into a specific resin, for example, an end-capturing agent can be used. For example, the structure represented by formula (1-1) or formula (2-1) described above can be introduced to the end of a carboxylic acid anhydride or acid anhydride derivative at the end of a resin by sealing it with a compound having a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members and a hydroxyl group, a thiol group, or an amino group as an end-sealing agent. From the viewpoint of reducing the molar amount of the nitrogen-containing heterocyclic structure that is detached from the resin when subjected to the aforementioned heating, it is preferable to use a compound having a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members and an amino group as such an end-captive. Furthermore, other end-capsulating agents, as described later, may be used simultaneously at this time. However, from the viewpoint of reducing the molar amount of the nitrogen-containing heterocyclic structure that detaches from the resin, it is also preferable not to use other end-capsulating agents.

[0159] Examples of compounds having a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members and an amino group include the compound represented by the following formula (T-1). [ka] In formula (T-1), L 1 , R 1 and n are, respectively, L in equation (1-1) above. 1 , R 1 This is synonymous with n, and the preferred embodiment is similar.

[0160] Alternatively, the above-mentioned nitrogen-containing heterocyclic structure may be introduced to the ends of a specific resin by encapsulating the amino group at the end of the resin with a compound having a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members and a functional group that can react with the amino group.

[0161] -Other end-capping agents- Examples of the end-capturing agents mentioned above include the following compounds. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin ends, suitable end-sealing agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. Monoalcohols, phenols, and monoamines are more preferable due to their reactivity and film stability. Preferred monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-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.Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capturing agents. Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0162] -Solid precipitation- The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[0163] [Specific examples] Specific examples of the specific resin include, but are not limited to, the specific resin used in the examples described later, or the specific resins in which the terminal structure of these resins has been changed to the specific example of a structure containing a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as ring members as described above.

[0164] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin or may contain two or more specific resins. When it contains two or more specific resins, it is preferable that the total amount is within the above range.

[0165] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above). 115 Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0166] <Other resins> The resin composition of the present invention may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Other resins include polyimide precursors different from the specified resin, polyimides different from the specified resin, polybenzoxazole precursors different from the specified resin, polybenzoxazoles different from the specified resin, polyamideimide precursors different from the specified resin, polyamideimides different from the specified resin, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -3 By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0167] If 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, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0168] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0169] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0170] 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 also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0171] 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.

[0172] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0173] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, among others. Examples of polyfunctional acrylates and methacrylates, as well as mixtures thereof, include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated; urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193; polyester acrylates as described in Japanese Unexamined Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490; and epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid. Compounds described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Publication No. 2008-292970 are also suitable. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond.

[0174] In addition, other preferred radical crosslinking agents besides those mentioned above include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent No. 4364216, etc., as well as cardo resins.

[0175] Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0176] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and these contents are incorporated herein.

[0177] Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylateing them, as described in Japanese Patent Publication No. 10-062986 with specific examples of formulas (1) and (2), can also be used as radical crosslinking agents.

[0178] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Publication No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein by reference.

[0179] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0180] Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include Ligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0181] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as 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. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0182] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0183] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0184] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (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, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0185] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0186] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0187] [Other crosslinking agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0188] Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0189] [ka]

[0190] R 100 This represents an alkyl group or acyl group. R 101 and R 102 Each of these independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0191] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

[0192] [ka]

[0193] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103 This includes hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or groups that decompose upon the action of an acid to produce alkali-soluble groups (for example, groups that are eliminated by the action of an acid, -C(R4 ) 2COOR 5 The group represented by (R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 The symbol indicates a group that is 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 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Groups that decompose under the action of acid to produce alkali-soluble groups, groups that are eliminated under the action of acid, -C(R 4 ) 2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 Examples include: In the formula, R 36 ~R 39 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 These elements may be joined together to form a ring. The alkyl group described above is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group described above may be linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those described above for preferred embodiments of alkyl and aryl groups. The above 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. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0194] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0195] Groups that decompose upon the action of an acid to produce alkali-soluble groups, or groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, tertiary alkyl ester groups and acetal groups.

[0196] The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule, but are not limited to these.

[0197] [ka]

[0198] [ka]

[0199] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0200] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0201] Specific examples of urea-based crosslinking agents include, for example, glycoluryl-based crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea. Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0202] Specific examples of benzoguanamine crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0203] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0204] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), 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, and TriML-35XL. Examples include 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 (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0205] Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0206] - Epoxy compounds (compounds containing epoxy groups) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0207] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0208] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 0-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, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0209] [ka]

[0210] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0211] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0212] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0213] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0214] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0215] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agents may be present by one type or by two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0216] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. It is particularly preferable that it contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

[0217] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -1 ·cm -1 It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0218] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0219] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0220] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0221] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0222] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0223] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose maximum absorption wavelength is matched to a light source of wavelength such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

[0224] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

[0225] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and KeycureVIS813 (manufactured by KingBrotherChem).

[0226] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0227] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0228] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)(imino))butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0229] [ka]

[0230] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0231] As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the details of which are incorporated herein by reference.

[0232] As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505, which are incorporated herein by reference.

[0233] Furthermore, oxime compounds containing a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 2013-164471, the details of which are incorporated herein by reference.

[0234] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein by reference. Another example of an oxime compound having a nitro group is ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0235] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0236] As photoradical polymerization initiators, oxime compounds in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0237] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1 An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0238] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. R X3 ~R X14 Each of these independently represents a hydrogen atom or a substituent; However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0239] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0240] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0241] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0242] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0243] Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0244] Furthermore, photoradical polymerization initiators can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal. In addition, compounds represented by the following formula (I) can also be used.

[0245] [ka]

[0246] 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 a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. I01 is a group represented by formula (II), or R I00 It is the same group as R I02 ~R I04 Each of these is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0247] [ka]

[0248] In the formula, R I05 ~R I07 This is R in equation (I) above. I02 ~R I04 It is the same as this.

[0249] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0250] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0251] If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0252] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenones, Michlaz ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyrans, and indigos. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0253] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0254] [Chain transport agent] The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0255] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0256] If the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0257] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator refers to a compound that generates at least one of a Brønsted acid and a Lewis acid upon irradiation with light in the 200 nm to 900 nm range. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photoacid generator is preferably capable of generating acid upon photosensitization. Preferred examples of acids that are generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diphosphate esters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0258] Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oximesulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoint of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the mechanical properties of the formed film, oxime esters are preferred.

[0259] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is bonded to a monovalent or polyvalent amino compound via a sulfonamide, and those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or sulfonamide. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds are to be substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By including such quinone diazide compounds, it is possible to obtain resin compositions that are sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays.

[0260] Specifically, hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisO CP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of such materials include, but are not limited to, Asahi Organic Chemicals Industry Co., Ltd.'s products: 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc.

[0261] Examples of amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0262] Furthermore, specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0263] Among these, it is preferable that the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.

[0264] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of resin. This range of quinone diazide compound content is preferable because it allows for higher sensitivity by obtaining a contrast between the exposed and unexposed areas. Furthermore, sensitizers and other additives may be added as needed.

[0265] The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but it is preferably an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later.

[0266] [ka]

[0267] In equation (OS-1), X 3 X represents an alkyl group, an alkoxy group, or a halogen atom. 3 If there are multiple instances, they may be the same or different. (See above X) 3 The alkyl and alkoxy groups in may have substituents.3 The alkyl group in is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 In X, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. 3 In this mixture, chlorine atoms or fluorine atoms are preferred as halogen atoms. In formula (OS-1), m3 represents an integer between 0 and 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 They may be the same or different. In equation (OS-1), R 34 represents an alkyl or aryl group, preferably 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, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. 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, an aryl group having 6 to 20 carbon atoms, or an aryl halide group having 6 to 20 carbon atoms.

[0268] In equation (OS-1), m3 is 3, and X 3 The group is a methyl group, X 3 The substitution position is the ortho position, R 34 Compounds in which the group is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group are particularly preferred.

[0269] Specific examples of oximesulfonate compounds represented by formula (OS-1) include the following compounds described in paragraphs 0064-0068 of Japanese Patent Publication No. 2011-209692 and paragraphs 0158-0167 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0270] [ka]

[0271] In formula (OS-103) ~ formula (OS-105), R s1 R represents an alkyl group, aryl group, or heteroaryl group, and there may be multiple R groups. s2 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and there may be multiple Rs. s6 Each of these independently represents a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group, or alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the above may have substituents known within the range in which the effects of the present invention can be obtained.

[0272] In formula (OS-103) ~ formula (OS-105), R s2 R is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. There may be two or more R in the compound. s2 It is preferable that one or two of these are alkyl groups, aryl groups, or halogen atoms, more preferably that one is an alkyl group, aryl group, or halogen atom, and particularly preferably that one is an alkyl group and the rest are hydrogen atoms. s2 The alkyl or aryl group represented by may have substituents known within the range that the effects of the present invention can be obtained. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0273] In formulas (OS-103) to (OS-105), ns represents either 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the above may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0274] Furthermore, the compound represented by formula (OS-103) is particularly preferably a compound represented by formula (OS-106), formula (OS-110), or formula (OS-111), the compound represented by formula (OS-104) is particularly preferably a compound represented by formula (OS-107), and the compound represented by formula (OS-105) is particularly preferably a compound represented by formula (OS-108) or formula (OS-109). [ka]

[0275] In formula (OS-106) ~ formula (OS-111), R t1 R represents an alkyl group, an aryl group, or a heteroaryl group. t7 R represents a hydrogen atom or a bromine atom. t8 R 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, a methoxymethyl group, a phenyl group, or a chlorophenyl group. t9 R represents a hydrogen atom, halogen atom, methyl group, or methoxy group. t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 This represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0276] In formula (OS-106) ~ formula (OS-111), R t8 This represents a hydrogen atom, a C1-C8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, preferably a C1-C8 alkyl group, more preferably a C1-C8 alkyl group, even more preferably a C1-C6 alkyl group, and particularly preferably a methyl group.

[0277] In formula (OS-106) ~ formula (OS-111), R t9 This represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom. R t2 This represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E,Z) of the oxime may be either one or a mixture. Specific examples of oximesulfonate compounds represented by formulas (OS-103) to (OS-105) above include the compounds described in paragraphs 0088 to 0095 of Japanese Patent Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0278] Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

[0279] [ka]

[0280] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or heteroaryl group. u9 A more preferable embodiment is that R is a cyano group or an aryl group. u9 A more preferable embodiment is one in which the group is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a This represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 Each of these independently represents an alkyl group or an aryl group.

[0281] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of these may bond to each other to form a ring. In this case, the ring may fused to form a fused ring with the benzene ring. u1 ~R u4 Preferably, R is a hydrogen atom, a halogen atom, or an alkyl group. u1 ~R u4 A configuration in which at least two of them bond to each other to form an aryl group is also preferred. u1 ~R u4 A configuration in which all of these atoms are hydrogen atoms is preferred. Each of the above substituents may have further substituents.

[0282] The compound represented by the above formula (OS-101) is more preferably the compound represented by the formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture of both. Specific examples of compounds represented by formula (OS-101) include those described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Chemical Co., Ltd.).

[0283] Furthermore, compounds represented by the following structural formula are also preferred examples. [ka]

[0284] Examples of organic halogenated compounds include those described in Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-32070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, and MPHutt, "Jurnal of Heterocyclic Chemistry" 1 (No. 3), (1970), and the contents of these publications are incorporated herein by reference. In particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds are preferred examples. More preferably, s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-tri Azine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) Phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0285] Examples of organoborate compounds include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Publication No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98. Proceeding April Organic borates as described in "19-22, 1998, Chicago," etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes as described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, organoboron iodonium as described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 Examples include organoboron phosphonium complexes described in Japanese Patent Publication No. 9-188710, organoboron transition metal coordination complexes described in Japanese Patent Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, and the contents of these are incorporated herein by reference.

[0286] Examples of disulfone compounds include those described in Japanese Patent Publication No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0287] Examples of the above onium salt compounds include diazonium salts described in SISchlesinger, Photogr.Sci.Eng., 18,387 (1974) and TSBal et al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055 and Japanese Patent Publication No. 4-365049, phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056, and iodonium salts described in European Patent Nos. 104 and 143, U.S. Patent Nos. 339,049 and 410,201, Japanese Patent Publication No. 2-150848 and Japanese Patent Publication No. 2-296514. Sulfonium salts as described in the specifications of European Patents No. 370,693, 390,214, 233,567, 297,443, and 297,442; U.S. Patents No. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827; German Patents No. 2,904,626, 3,604,580, and 3,604,581; JVCrivello Examples include selenonium salts described in et al, Macromolecules, 10(6), 1307 (1977) and JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), as well as onium salts such as arsonium salts and pyridinium salts described in CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and these contents are incorporated herein by reference.

[0288] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [ka] In equation (RI-I), Ar 11Z represents an aryl group having 20 or fewer carbon atoms, which may have 1 to 6 substituents. Preferred substituents include C1-C12 alkyl groups, C2-C12 alkenyl groups, C2-C12 alkynyl groups, C6-C12 aryl groups, C1-C12 alkoxy groups, C1-C12 aryloxy groups, halogen atoms, C1-C12 alkylamino groups, C2-C12 dialkylamino groups, alkylamide groups of the alkyl group having 1 to 12 carbon atoms or arylamide groups of the aryl group having 6 to 20 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups, and C1-C12 thioaryl groups. 11 - represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar 21 Ar 22 Each of these independently represents an aryl group having 1 to 20 carbon atoms, which may have 1 to 6 substituents. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z21 -R represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R 31 , R 32 , R 33 Each of these represents an aryl group or alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may each have 1 to 6 substituents independently. Preferably, from the viewpoint of reactivity and stability, it is an aryl group. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group independently, alkylamide groups or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 31 - ∫ represents a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion. From the standpoint of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or carboxylate ion are preferred.

[0289] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka] [ka]

[0290] The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, relative to the total solid content of the resin composition. The photoacid generator may be used alone or in combination of multiple types. In the case of a combination of multiple types, it is preferable that their total amount is within the above range. Furthermore, it is preferable to use it in combination with a sensitizer in order to impart photosensitivity to the desired light source.

[0291] <Base Generator> The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of nonionic base-generating compounds include those represented by formulas (B1), (B2), or (B3). [ka]

[0292] In equations (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Each of these is independently an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 They cannot become hydrogen atoms at the same time. Also, Rb 1 , Rb 2 and Rb 3 None of these have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply when the bonded carbon atom forms a carbonyl group, i.e., when it forms an amide group together with the nitrogen atom.

[0293] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0294] More specifically, Rb 1 and Rb 2 The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that provides the effects of the present invention. Rb 1 and Rb 2 These may be bonded to each other to form a ring. A preferred ring is a 4-7 member nitrogen-containing heterocycle. Rb 1 and Rb 2 In particular, it is preferable that the alkyl group is a linear, branched, or cyclic alkyl group which may have substituents (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have substituents (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have substituents.

[0295] Rb 3Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb 3 It may further have substituents to the extent that it exhibits the effects of the present invention.

[0296] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2). [ka]

[0297] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 These are, respectively, Rb in equation (B1). 1 and Rb 2 It is the same as this. Rb 13The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents within a range that provides the effects of the present invention. In particular, Rb 13 An aryl alkyl group is preferred.

[0298] Rb 33 and Rb 34 Each of these is independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably 2 to 8, and still more preferably 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0299] Rb 35 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0300] Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a). [ka]

[0301] Rb 11 and Rb 12Rb in equation (B1-1) 11 and Rb 12 It is synonymous with [the above]. Rb 15 and Rb 16 The group is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and still more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and still more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and still more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and still more preferably with 7 to 11 carbon atoms), with a hydrogen atom or a methyl group being preferred. Rb 17 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0302] [ka]

[0303] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen and carbon atoms, and having 3 or more atoms on the linking chain pathway. N1 and R N2 Each of these independently represents a monovalent organic group.

[0304] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that links these linked objects in the shortest possible distance (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4. [ka]

[0305] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even 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 carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0306] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1). [ka]

[0307] In formula (N1), R N1 and R N2 Each of these independently represents a monovalent organic group, R C1 represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0308] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0309] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with an aliphatic hydrocarbon group being preferred. N1 and R N2 Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0310] R N1 and R N2Examples of aliphatic hydrocarbon groups that constitute the linear alkyl group include linear or branched alkyl groups, cyclic alkyl groups, groups relating to a combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched alkyl groups are preferably those having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like. The cyclic alkyl group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. The group comprising the combination of a linear alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups comprising the combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the perspective of raising the boiling point of the decomposition product bases described later, R N1 and R N2 A C5-C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1-C8 alkyl group is preferred.

[0311] R N1 and R N2These may be linked together to form a cyclic structure. In forming a cyclic structure, oxygen atoms, etc., may be present in the chain. Also, R N1 and R N2 The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0312] R C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

[0313] As a protecting group, a protecting group that decomposes upon the action of an acid or a base is preferred, and a protecting group that decomposes with an acid is particularly preferred.

[0314] Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0315] There are no specific requirements for the divalent linking group constituting L, but hydrocarbon groups are preferred, and aliphatic hydrocarbon groups are more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferable to have a divalent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, or a group which is a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0316] The preferred linking group L is specifically a linear or branched linear alkylene group, a cyclic alkylene group, a group relating to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched alkylene group is preferably composed of 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. The combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0317] The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group is preferably one with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0318] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0319] [ka]

[0320] The molecular weight of the nonionic base 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.

[0321] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0322] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0323] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0324] If the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range.

[0325] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0326] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0327] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0328] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0329] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0330] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0331] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0332] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0333] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0334] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0335] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0336] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

[0337] The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total number is within the above range.

[0338] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0339] [Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062-0073 of Japanese Patent Publication No. 2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060-0061 of Japanese Patent Publication No. 2014-191252, the compounds described in paragraphs 0045-0052 of Japanese Patent Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067-0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0340] [ka]

[0341] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0342] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0343] Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0344] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content falls within the above range.

[0345] <Migration inhibitor> The resin composition of the present invention may further contain a migration inhibitor. The compounds that fall under the category of the specified resins mentioned above are not considered migration inhibitors. By including a migration inhibitor, it becomes possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

[0346] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0347] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0348] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0349] Furthermore, as a microcation inhibitor, the compound may contain a nitrogen-containing compound that includes a nitrogen-containing heterocycle and an amino group within the same compound, where one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms that are ring members of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group. In the above nitrogen-containing compound, it is preferable that at least one of the nitrogen atoms that are ring members is directly bonded to the carbonyl group. By including such compounds, it may be possible to further improve the adhesion between the metal and the hardened film even after a long period of time.

[0350] Specific examples of migration inhibitors include the following compounds.

[0351] [ka]

[0352] If the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition of the present invention.

[0353] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0354] <Polymerization inhibitors> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0355] Specific polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine monocerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and compounds described in paragraphs 0031-0046 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0356] If 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, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

[0357] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0358] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, an acid scavenger refers to a compound that can capture generated acids when present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferred, such as primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides, with primary amines, secondary amines, tertiary amines, and ammonium salts being preferred, and secondary amines, tertiary amines, and ammonium salts being more preferred. Preferred acid scavengers include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure; alkylamine derivatives having a hydroxyl group and / or an ether linkage; and aniline derivatives having a hydroxyl group and / or an ether linkage. When an onium structure is present, the acid scavenger is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than the acid generated by the acid generator.

[0359] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, and 1,8-diazabicyclo[5,4,0]undeker7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether linkage include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether linkage include N,N-bis(hydroxyethyl)aniline.

[0360] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylammonium hydroxide Examples include methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0361] These acid scavengers may be used individually or in combination of two or more types. The composition according to the present invention may or may not contain an acid scavenger. If it does contain an acid scavenger, the amount of acid scavenger is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0362] The ratio of acid generator to acid scavenger used is preferably 2.5 to 300 in molar ratio. Specifically, a molar ratio of 2.5 or higher is preferred from the viewpoint of sensitivity and resolution, and 300 or lower is preferred from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time from exposure to heat treatment. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0363] <Other additives> The resin composition of the present invention may contain various additives as needed, to the extent that the effects of the present invention are obtained, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregating agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, it is preferable that their total amount is 3% by mass or less of the solid content of the resin composition of the present invention.

[0364] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0365] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the efficiency of the liquid can be further improved. Specifically, when forming a film using a coating solution to which a surfactant-containing composition has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0366] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (all manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (all manufactured by 3M Corporation) Examples include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Corporation), etc. As fluorine-based surfactants, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503 may also be used, and the contents of these are incorporated herein. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Publication No. 2011-89090, the details of which are incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0367] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0368] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0369] 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, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BIC Chemie Co., Ltd.).

[0370] Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalgen 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. (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0371] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0372] Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0373] Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0374] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0375] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

[0376] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0377] When the resin composition of the present invention contains 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. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0378] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals in response to thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0379] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0380] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0381] [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0382] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter for inorganic particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using NanotracWAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement methods are difficult, measurements can also be performed using centrifugal sedimentation, X-ray transmission, or laser diffraction / scattering methods.

[0383] [UV absorber] The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate, while examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0384] Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy(hydroxy) Examples include bis(hydroxyphenyl)triazine compounds such as c-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0385] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[0386] [Organotitanium compounds] The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0387] Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, 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-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0388] In particular, from the viewpoint of achieving better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0389] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0390] [Antioxidant] The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group within the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent Publication No. 6268967 may also be used as antioxidants, and this information is incorporated herein by reference. Additionally, the compositions of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, thereby removing the protecting group.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by formula (3).

[0391] [ka]

[0392] In general formula (3), R 5 R represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 k represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2-10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0393] The compound represented by formula (3) suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

[0394] Since it can act on both the resin and the metal material simultaneously, k is more preferably an integer between 2 and 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may also have substituents. Among these, alkyl ether groups and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

[0395] Examples of compounds represented by general formula (3) include the following, but are not limited to the structures shown below.

[0396] [ka]

[0397] [ka]

[0398] [ka]

[0399] [ka]

[0400] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[0401] [Anti-coagulation agent] The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

[0402] In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-flocculation agent. If it does contain an anti-flocculation agent, the amount of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[0403] [Phenol compounds] The resin composition of this embodiment may optionally contain phenolic compounds. 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 (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0404] In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination. The composition of the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content of the composition of the present invention.

[0405] [Other polymer compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0406] In this invention, the other polymer compounds may be used individually or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. If other polymer compounds are included, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition of the present invention.

[0407] <Properties of resin compositions> 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 coating film thickness, 1,000 mm 2 / s~12,000mm 2 / s is preferred, and 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500mm 2 / s~8,000mm 2 / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm 2 If the rate is 1 / s or higher, it is easy to coat the film thickness required for, for example, as an insulating film for rewiring, and 12,000 mm2 If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0408] <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 is improved. Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

[0409] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm (parts per million) by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0410] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0411] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. Methods for adjusting the halogen atom content include ion exchange treatment.

[0412] Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0413] <Cured product of resin composition> A cured product of the resin composition of the present invention can be obtained by curing the resin composition. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The curing of the resin composition is preferably by heating, more preferably within the range of 120°C to 400°C, even more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing heat dissipation functions. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention upon curing 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 change in volume of the resin composition before and after curing, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

[0414] <Characteristics of cured resin compositions> The imidization reaction rate of the cured 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, the cured product may have excellent mechanical properties. The elongation at break of the cured 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.

[0415] <Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing can be achieved using methods such as mixing with agitators, mixing with a ball mill, or mixing by rotating the tank itself. The mixing temperature is preferably 10-30°C, and more preferably 15-25°C.

[0416] Furthermore, it is preferable to perform filtration using a filter to remove foreign matter such as dirt and fine particles from the resin composition of the present invention. The filter pore size can be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm may be connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm may be connected in series as the second stage. In addition, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. In addition, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent. A combination of filter filtration and impurity removal using an adsorbent may also be used. As the adsorbent, any known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. Furthermore, after filtration using a filter, the resin composition filled into the bottle may be subjected to a degassing process by placing it under reduced pressure.

[0417] (Method of manufacturing a cured product) The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. Furthermore, the method for producing a cured product of the present invention more preferably includes the above-mentioned film formation step, an exposure step for selectively exposing the film formed in the film formation step, and a developing step for developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product of the present invention is particularly preferably to include at least one of the above-mentioned film formation step, exposure step, development step, and a heating step for heating the pattern obtained in the development step and a post-development exposure step for exposing the pattern obtained in the development step. Furthermore, the manufacturing method of the present invention may also preferably include the above-mentioned film formation step and the step of heating the above-mentioned film. The details of each step are explained below.

[0418] <Film formation process> The resin composition of the present invention can be used in a film-forming process, where it is applied to a substrate to form a film. The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film.

[0419] [Base material] The type of substrate can be appropriately determined depending on the application, but examples include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin-film transistor) array substrates, mold...

Claims

1. A resin comprising at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors, The resin comprises a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, The ratio of the molar amount of the nitrogen-containing heterocyclic structure that is detached from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin is 10% or less. The resin includes a structure represented by the following formula (1-1) or formula (2-1): Resin composition. 【Chemistry 1】 In formula (1-1), L1 represents an n+1 valent linking group that does not contain a single bond or an imide ring structure, R1 represents a nitrogen-containing heterocyclic structure that contains two or more nitrogen atoms as ring members, n is an integer of 1 or more, and * represents a bonding site with another structure. In formula (2-1), L2 represents an m+1 valent linking group that does not contain a single bond or an oxazole ring structure, R2 represents a nitrogen-containing heterocyclic structure that contains two or more nitrogen atoms as ring members, m is an integer of 1 or more, and * represents a bonding site with another structure.

2. A resin comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, and polyamideimide, and a photopolymerization initiator. The resin comprises a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, The ratio of the molar amount of the nitrogen-containing heterocyclic structure that is detached from the resin when the resin is heated at 1 atmosphere, 350°C, and 2 hours to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin is 10% or less. The resin includes a structure represented by the following formula (1-1) or formula (2-1): Resin composition. 【Chemistry 2】 In formula (1-1), L1 represents an n+1 valent linking group that does not contain a single bond or an imide ring structure, R1 represents a nitrogen-containing heterocyclic structure that contains two or more nitrogen atoms as ring members, n is an integer of 1 or more, and * represents a bonding site with another structure. In formula (2-1), L2 represents an m+1 valent linking group that does not contain a single bond or an oxazole ring structure, R2 represents a nitrogen-containing heterocyclic structure that contains two or more nitrogen atoms as ring members, m is an integer of 1 or more, and * represents a bonding site with another structure.

3. The resin composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic structure is present at the end of the resin.

4. comprising at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors, The resin includes a structure represented by the following formula (1-1) or formula (2-1). Resin composition. 【Transformation 3】 In formula (1-1), L １ R is a linking group that does not contain a single bond or an imide ring structure, n+1 valent １ * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer of 1 or more, and * represents a bonding site with other structures. In formula (2-1), L ２ R is a linking group that does not contain a single bond or an oxazole ring structure, ２ represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures.

5. A resin comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, and polyamideimide, and a photopolymerization initiator. The resin includes a structure represented by the following formula (1-1) or formula (2-1). Resin composition. 【Chemistry 4】 In formula (1-1), L １ R is a linking group that does not contain a single bond or an imide ring structure, n+1 valent １ * represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, n is an integer of 1 or more, and * represents a bonding site with other structures. In formula (2-1), L ２ R is a linking group that does not contain a single bond or an oxazole ring structure, ２ represents a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as ring members, m represents an integer of 1 or more, and * represents a bonding site with other structures.

6. The resin composition according to any one of claims 1 to 5, wherein the content of nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as ring members is 0.001 to 10% by mass, relative to the total solid content of the composition.

7. The resin composition according to any one of claims 1 to 6, wherein the nitrogen-containing heterocyclic structure contained in the resin comprises an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton.

8. The resin composition according to any one of claims 1 to 7, wherein the weight-average molecular weight of the resin is 1,500 to 70,000.

9. A resin composition according to any one of claims 1 to 8, used for forming an interlayer insulating film for a redistribution layer.

10. A cured product obtained by curing the resin composition according to any one of claims 1 to 9.

11. A laminate comprising two or more layers of the cured material described in claim 10, wherein a metal layer is included between any of the cured materials.

12. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1 to 9 to a substrate to form a film.

13. A method for producing a cured product according to claim 12, comprising an exposure step of exposing the film to light and a developing step of developing the film.

14. A method for producing a cured product according to claim 12 or 13, comprising a heating step of heating the film to 50 to 450°C.

15. A semiconductor device comprising a cured product according to claim 10 or a laminate according to claim 11.

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