Resin composition, cured product, laminate, method for producing the cured product, and semiconductor device

Abstract

A resin composition which includes a precursor of a cyclization-product resin and satisfies the following requirement 1 and / or requirement 2; 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. Requirement 1: To contain compound B, which has both a group that generates an acid group by the action of heat and / or light and a group that generates a base by the action of an acid. Requirement 2: To contain both compound C, which has a group that generates an acid group by the action of heat and / or light and which differs from the compound B, and compound D, which has a group that generates a base by the action of an acid.

Description

[Technical field]

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

[0002] Cyclized resins such as polyimides are used in various applications due to their excellent heat resistance and insulating properties. The applications include, but are not limited to, materials for insulating films and sealing materials, or protective films for semiconductor devices for mounting. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the above-mentioned applications, the cyclized resin, such as a polyimide, is used in the form of a resin composition that includes a precursor of the cyclized resin, such as a polyimide precursor. Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. The precursor of the cyclized resin, such as the polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product. Since the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc., of the applied resin composition. In addition to the high performance of cyclized resins such as polyimide, from the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned resin composition is expected to continue.

[0004] For example, Patent Document 1 describes a photosensitive resin composition that contains a polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent, in which the polybenzoxazole precursor is a polybenzoxazole precursor in which at least a portion of the phenolic hydroxyl groups are protected with acid-decomposable groups, and the thermal base generator is a compound having a specific structure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2016-212380 A Summary of the Invention [Problem to be solved by the invention]

[0006] In cured products made from resin compositions, there is a demand for both improved storage stability of the composition and improved elongation at break of the resulting cured products.

[0007] The present invention aims to provide a resin composition having excellent storage stability and excellent breaking elongation of the resulting cured product, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. [Means for solving the problem]

[0008] Examples of typical embodiments of the present invention are given below. <1> A resin composition comprising a precursor of a cyclized resin and satisfying at least one of the following conditions 1 and 2: Condition 1: the resin composition contains a compound B having a group that generates an acid group when acted on by at least one of heat and light, and a group that generates a base when acted on by an acid; Condition 2: The resin composition contains compound C, which has a group that generates an acid group when acted on by at least one of heat and light and is different from compound B, and compound D, which has a group that generates a base when acted on by acid. <2> In the above-mentioned compound B and compound C, the group which generates an acid group by the action of at least one of heat and light contains a protected carboxy group, a phenolic hydroxyl group, or a sulfonic acid group. <1> The resin composition according to claim 1. <3> The compound B is a compound represented by any one of the following formulas (1-1), (1-2), and (1-3): <1> or <2> The resin composition according to claim 1. [ka] In formulas (1-1) to (1-3), R 1 ~R 5 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 1 , two R 2 , the three R's 3 Two or three of the following, two R 4 , or two R 4 One or two of these and R 5 may be bonded to form a ring structure. <4> The compound B is a compound represented by any one of the following formulas (2-1), (2-2), (2-3) and (2-4): <1> or <2> The resin composition according to claim 1. [ka] In formulas (2-1) to (2-4), R 6 ~R 11 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 6 , two R 7 ,The three R's 8 Two or three of the following, two R 9 , or two R 9 One or two of these and R 10 may be bonded to form a ring structure. <5> The compound B is a compound represented by any one of the following formulas (3-1), (3-2) and (3-3): <1> or <2> The resin composition according to claim 1. [ka] In formulas (3-1) to (3-3), R 12 ~R 16each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 12 , two R 13 , two R 13 At least one of and R 14 , the three R's 15 Two or three of the following, two R 16 may be bonded to form a ring structure. <6> Further comprising a photoinitiator; <1> ~ <5> 10. The resin composition according to claim 9 . <7> Contains a polymerizable compound, <1> ~ <6> 10. The resin composition according to claim 9 . <8> The amount of acid groups contained in the composition per 1 g of the resin composition of the present invention is 1.0 to 15.0 mg KOH / g. <1> ~ <7> 10. The resin composition according to claim 9 . <9> <1> ~ <8> 2. A cured product obtained by curing the resin composition according to claim 1. <10> <9> 1. A laminate comprising two or more layers of the cured product according to claim 1, and a metal layer between any two of the layers of the cured product. <11> <1> ~ <8> 13. A method for producing a cured product, comprising: a film formation step of applying the resin composition according to any one of the above items 1 to a substrate to form a film. <12> The method includes an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern. <11> A method for producing the cured product according to claim 1. <13> The film is heated at 50 to 450 ° C. <11> or <12> A method for producing the cured product according to claim 1. <14> <9> or <10> A semiconductor device comprising the stack according to claim 1. Effect of the Invention

[0009] According to the present invention, there are provided a resin composition having excellent storage stability and excellent breaking elongation of the resulting cured product, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect. In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulae represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction. In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the 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 atm), and the relative humidity is 50% RH. As used herein, combinations of preferred aspects are more preferred aspects.

[0011] (Resin composition) The resin composition of the present invention contains a precursor of a cyclized resin (hereinafter, also referred to as a “specific resin”) and satisfies at least one of the following conditions 1 and 2. Condition 1: the resin composition contains a compound B (hereinafter, also simply referred to as “compound B”) having a group that generates an acid group when acted on by at least one of heat and light, and a group that generates a base when acted on by an acid; Condition 2: The resin composition contains a compound C (hereinafter also simply referred to as "compound C") which has a group that generates an acid group when acted upon by at least one of heat and light and is a compound different from the compound B, and a compound D (hereinafter also simply referred to as "compound D") which has a group that generates a base when acted upon by an acid.

[0012] The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development. In the present invention, negative development refers to a development in which the non-exposed areas are removed by development during exposure and development, and positive development refers to a development in which the exposed areas are removed by development. As the above-mentioned exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.

[0013] The resin composition of the present invention is excellent in storage stability of the composition and in elongation at break of the resulting cured product. The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

[0014] Conventionally, resin compositions containing a cyclized resin precursor and a base generator have been investigated. In the precursor of a cyclized resin such as a polyimide precursor, a cyclization reaction such as imidization proceeds due to the action of a base. By utilizing this property, a film containing a resin composition having a precursor of a cyclized resin and a base generator is formed, and then a high-temperature heat treatment or the like is performed, so that a cured product containing a cyclized resin having high heat resistance and high mechanical properties can be obtained. On the other hand, it has been found that when such a composition is stored, a small amount of a basic compound is generated in the liquid composition, and a cyclization reaction of a precursor of a cyclized resin proceeds in the composition. This reduces the solubility of the cyclized resin precursor in a solvent, causing problems such as precipitation of the resin in the composition. In the precursor of the cyclized resin, cyclization is promoted under basic conditions, so that cyclization can be inhibited by adjusting the composition to an acidic condition. However, if a large amount of base is generated during storage, even if the composition is acidic during preparation, the action of the base in the composition will promote cyclization, and it may be difficult to obtain storage stability (also referred to as the preservation stability of the composition) by simply adjusting the composition to an acidic state. The resin composition of the present invention contains a precursor of a cyclized resin and compound B, or compounds C and D. That is, in the present invention, the generation of a base is contributed by an acid group generated by the action of heat or light. Here, it is believed that by using an embodiment in which acid groups are generated by the action of heat or light as described above and the acid groups promote the generation of a base, compound decomposition and base generation in the composition can be suppressed. Furthermore, when heat or light is applied, an acid group is rapidly generated, and then a base is rapidly generated, so that the cyclization reaction in the precursor of the cyclized resin can be promoted. From the above, it is believed that the resin composition of the present invention can achieve both high levels of storage stability of the composition and high levels of breaking elongation after film curing. In addition, by using a compound that generates an acid group by the action of at least one of heat and light, such as compound B or compound C, it is possible to design a resist with a low acid value, which will be described later, in a state in which no exposure to heat or light is performed. This is thought to easily suppress migration of metals such as copper, and to provide a cured film with excellent adhesion.

[0015] Furthermore, the resin composition of the present invention satisfies at least one of the above-mentioned conditions 1 and 2. When condition 1 is satisfied, compound B has a group that generates an acid group by the action of at least one of heat and light and a group that generates a base by the action of an acid in the same molecule, so it is considered that when an acid group is generated, a base can be generated quickly. In other words, it is considered that the base generation efficiency can be increased, and for example, the amount of base generated is large even at a low temperature. It is presumed that this makes it possible to cyclize the specific resin at a low temperature. When condition 2 is satisfied, compound C that generates an acid group and compound D that generates a base are different molecules, and therefore it takes time for the base generated from compound D to be quenched by the acid group present in compound C, and it is considered that the life of the base is extended. As a result, for example, the number of cyclization reactions of a specific resin catalyzed by the generated base increases, and it is presumed that the cyclization of the resin can be sufficiently advanced with a smaller addition amount. The resin composition of the present invention may satisfy both of the above-mentioned conditions 1 and 2. That is, the resin composition may contain compound B, compound C, and compound D. When the resin composition of the present invention satisfies the above-mentioned condition 1, the resin composition of the present invention may contain compound B and compound C for the purpose of promoting the generation of a base from compound B, etc.

[0016] However, Patent Document 1 does not disclose a resin composition that contains a precursor of a cyclized resin and satisfies at least one of the above-mentioned conditions 1 and 2. The components contained in the resin composition of the present invention will be described in detail below.

[0017] <Specific resin> The resin composition of the present invention contains a precursor of a cyclized resin (specific resin). The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonding chain in a resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide. The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred. Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, the resin composition of the present invention preferably contains, as the specific resin, at least one type of resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. In addition, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, more preferably contains a radical polymerization initiator described later and also contains a radical crosslinking agent described later. If necessary, the resin composition of the present invention may further contain a sensitizer described later. For example, a negative photosensitive film is formed from such a resin composition of the present invention. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. For example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed from the resin composition of the present invention.

[0018] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in terms of its type, but it preferably contains a repeating unit represented by the following formula (2). [ka] In formula (2), A 1 and A 2 each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0019] A in Equation (2) 1 and A 2 each independently represents an oxygen atom or -NH-, and is preferably an oxygen atom. R in Equation (2) 111represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. 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 group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Here, each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

[0020] R 111 is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it is preferable that the diamine contains 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 group consisting of a combination thereof, and it is more preferable that the diamine contains an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

[0021] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from these combinations, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-, and still more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0022] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 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 isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 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'-diaminodiphenyl sulfone, 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, esters 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,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)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl can be mentioned.

[0023] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0024] In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598 are also preferably used.

[0025] R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained organic film. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination 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 which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0026] Also, R 111From the viewpoint of i-line transmittance, it is preferable that the divalent organic group represented by the following formula (51) or formula (61) is used. In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that the divalent organic group represented by the formula (61) is used. Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group; R 50 ~R 57 At least one of these is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 each independently represents a fluorine atom, a methyl group, or a trifluoromethyl group, and each * 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, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0027] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), each * independently represents a bonding site to another structure. [ka] In formula (5), R 112 represents a single bond or a divalent linking group and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, a group selected from -O-, -CO-, -S-, -SO2-, -NHCO-, and a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a group selected from -O-, -CO-, -S-, and -SO2-, 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-.

[0028] R 115 Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. 115 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. The tetracarboxylic dianhydride is 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 formula (2) is 115 The same definition and preferred range are also the same.

[0029] Specific examples of tetracarboxylic dianhydrides 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'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-Benzophenonetetracarboxylic 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, 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 their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0030] Further, preferred examples include the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598.

[0031] In formula (2), R 111 and R 115At least one of R may have an OH group. 111 Examples of the residue include residues of bisaminophenol derivatives.

[0032] R in Equation (2) 113 and R 114 Each of R 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. 113 and R 114 It is preferable that at least one of R contains a polymerizable group, and it is more preferable that both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the above groups 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 is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically 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. The radically polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically 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), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0033] [ka]

[0034] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201 Examples of the alkylene group include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CHCH(OH)CH-, and polyalkyleneoxy group, of which alkylene groups such as ethylene group and propylene group, -CHCH(OH)CH-, cyclohexyl group, and polyalkyleneoxy group are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy group are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.

[0035] In formula (2), R 113 is a hydrogen atom, or R 114 When 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.

[0036] In formula (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0037] It is also 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 20% by mass or less.

[0038] In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be used as the diamine.

[0039] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it is possible to further widen the width of 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 independently represents a divalent organic group; R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; R 113 and R 114 At least one of the groups is a group containing a polymerizable group, and it is preferable that both of the groups are groups containing a polymerizable group.

[0040] A 1 , A 2 , R 111 , R 113 and R 114 Each independently represents A in formula (2). 1 , A 2 , R 111 , R 113 and R114 The same definition and preferred range are also the same. R 112 is R in Eq. (5). 112 The same definition and preferred range are also the same.

[0041] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, it may contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0042] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The 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 total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be the repeating unit represented by formula (2).

[0043] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight / number average molecular weight. In addition, when the resin composition contains multiple 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. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.

[0044] [Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit 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 independently represents a hydrogen atom or a monovalent organic group.

[0045] In formula (3), R 123 and R 124 are R in Eq. (2), 113 In other words, it is preferable that at least one of them is a polymerizable group. In formula (3), R 121 R represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. 121 The dicarboxylic acid residue is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types of dicarboxylic acid residues may be used.

[0046] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred. The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH. 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. Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic 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. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

[0047] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0048] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group having an aromatic group and two -COOH groups are more preferred.

[0049] [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 each * independently represents a bonding site to another structure.

[0050] Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0051] In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group is R 115 The same definition and preferred range are also the same. R 122is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols may be used alone or in combination.

[0052] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0053] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, or -NHCO-, and * and # each represent a bonding site with another structure. 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. 122 It is also preferable that R is a structure represented by the above formula. 122is a structure represented by the above formula, any two of the four * and # are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the other two are R 122 is preferably a bonding site with the oxygen atom to which the bond is bonded, and the two * are preferably R 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 is a bonding site with the nitrogen atom to which it is bonded, or two * are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the two #'s are R 122 is more preferably a bonding site with the oxygen atom to which the bond is bonded, and two * are 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 It is more preferable that the nitrogen atom to which the group is bonded is the bonding site.

[0054] The bisaminophenol derivative is also preferably a compound represented by the formula (As). [ka]

[0055] 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 the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

[0056] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

[0057] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at R3, is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, which is particularly preferred in that the effect of achieving a high cyclization rate when cured at low temperatures is further enhanced.

[0058] In addition, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, since this maintains the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

[0059] In the formula (As), R1 is more preferably alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene pertaining to R1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in that they can provide a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining the effects of high transparency to i-line and high cyclization rate when cured at low temperature.

[0060] For the production method of the bisaminophenol derivative represented by the above formula (As), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

[0061] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Of course, it goes without saying that the present invention is not limited to these.

[0062] The polybenzoxazole precursor may contain 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 the occurrence of warping due to ring closure can be suppressed.

[0063] [ka] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and a+b is 100 mol %.

[0064] In formula (SL), preferred Z is R in the b structure. 5s and R 6s is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, 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 of the polybenzoxazole precursor after dehydration ring closure, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

[0065] When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Examples of such a tetracarboxylic acid residue include R 115 Examples include:

[0066] The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. In addition, when the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as one resin are each within the above ranges.

[0067] [Polyamide-imide precursor] The polyamideimide precursor preferably contains a repeating unit 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.

[0068] In formula (PAI-2), R 117is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a straight-chain 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 in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group 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 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 more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0069] Also, R 117is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two of the carboxy groups may be converted into acid anhydrides. The optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0070] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing 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 in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0071] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0072] In formula (PAI-2), R 111 , A 2 , R113 are R in the above formula (2), 111 , A 2 , R 113 The same applies to the preferred embodiments.

[0073] The polyamideimide precursor may further comprise other repeat units. Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1). [ka]

[0074] In formula (PAI-1), R 116 represents a divalent organic group, R 111 represents a divalent organic group. In formula (PAI-1), R 116 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a straight-chain 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 in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group 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 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 more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0075] Also, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound. The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0076] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing 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 in which two or more of these are combined via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0077] Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic 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, sebacic acid, and hexadecafluorosuccinic acid. Examples of the fluorosebacic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

[0078] In formula (PAI-1), R 111 is R in the above formula (2). 111 The same applies to the preferred embodiments.

[0079] It is also preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0080] In order to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, the polyamide-imide precursor may be copolymerized with bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like, as the diamine component.

[0081] An embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The 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 total content is not particularly limited, and all of the repeating units in the polyamideimide precursor except for the terminals may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. The 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 total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals may be either the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

[0082] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the resin composition contains multiple types of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide precursor are within the above range. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimide precursors as one resin are each within the above range.

[0083] [Method for producing polyimide precursor, etc.] The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, is more preferable. Examples of the condensing agent 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 agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0084] -End capping agent- In the method for producing a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Preferred examples of monoalcohol compounds 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 phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound 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 of the amino groups 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 a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents. In addition, when the amino group at the resin end is blocked, it can be blocked with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. Preferred examples of the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0085] -Solid precipitation- The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain polyimide precursors and the like. In order to improve the degree of purification, the polyimide precursors and the like may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[0086] [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. 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 type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0087] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R 115 It is preferable that the polyimide precursor contains two or more different polyimide precursors.

[0088] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin"). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin having a molecular weight of at least 100 mol / g to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0089] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition. In addition, as a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still 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 content is not particularly limited, and may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0090] <Compound B> When the resin composition of the present invention satisfies condition 1, the resin composition of the present invention contains compound B having a group that generates an acid group when acted on by at least one of heat and light, and a group that generates a base when acted on by an acid. When the resin composition of the present invention satisfies the condition 2, the resin composition of the present invention may further contain the compound B described above.

[0091] [Group that generates an acid group by the action of at least one of heat and light] The group in compound B that generates an acid group when acted upon by at least one of heat and light is one in which 30 mol % or more of compound B is decomposed to generate an acid group when compound B is placed in a pressure-resistant capsule and heated at 230°C under 1 atmosphere (101,325 Pa) for 3 hours, or a solution obtained by mixing and dissolving 2 parts by mass of compound B, 30 parts by mass of polymethyl methacrylate, and 68 parts by mass of γ-butyrolactone is spin-coated on a substrate to form a film with a thickness of 5 μm, and the entire film is irradiated with light of any one of wavelengths from 254 to 450 nm at 500 mJ / cm. 2 When irradiated with an exposure dose of 1000 mol / s, 30 mol % or more of the compound is decomposed to generate an acid group.

[0092] In compound B, the group that generates an acid group by the action of at least one of heat and light preferably contains a protected acid group, more preferably contains a protected carboxy group, a protected phenolic hydroxyl group, or a protected sulfonic acid group, and further preferably contains a protected carboxy group. The structure in which the acid group is protected is not particularly limited, and a structure in which the acid group is protected by a known protecting group is used, and examples of the structure include a secondary ester group, a tertiary ester group, an acetal group, an alkoxycarbonyloxy group (e.g., a t-butoxycarbonyloxy group), etc.

[0093] In compound B, the pKa of the acid group generated by the action of at least one of heat and light is preferably −5 to 11, and more preferably 2 to 11. The pKa of the acid group can be calculated using the software package Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs. In this specification, pKa refers to the value calculated by the above software package unless otherwise specified. Furthermore, when the acid group has multiple pKa's, it is preferable that at least one of the pKa's falls within the above range.

[0094] The number of groups in compound B that generate an acid group by the action of at least one of heat and light is preferably 1 to 4, more preferably 1 or 2, and may be 1.

[0095] Specific examples of the group that generates an acid group when acted upon by at least one of heat and light include, but are not limited to, the following structures, in which * represents a bonding site with another structure. [ka]

[0096] [Group that generates a base when acted upon by an acid] The group in compound B that generates a base when acted on by an acid includes a compound having a basic group protected by an acid-decomposable group. The basic group protected by an acid-decomposable group is not particularly limited, but is preferably a group containing an amide structure. The amide structure is preferably a structure that is decomposed by the action of an acid to generate a base.

[0097] The base generated from compound B by the action of an acid is preferably an amine, more preferably a secondary amine or a tertiary amine. Furthermore, these bases may further react with other compounds in the composition to form bases or basic salts having different structures. In addition, the base generated from compound B by the action of an acid has a pKa of the conjugate acid of preferably 0 or more, more preferably 5 or more, and even more preferably 10 or more. There is no particular upper limit, but it is more preferably 30 or less. pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. When the conjugate acid has a plurality of pKa values, it is preferable that at least one of them is within the above range.

[0098] The base generated from compound B by the action of an acid may be a base having only one basic group, or may be a base having two or more basic groups. Furthermore, the number of molecules of base generated from compound B by the action of an acid may be one or more.

[0099] The molecular weight of the base generated from compound B by the action of an acid is preferably 50-300, more preferably 80-250, and further preferably 100-220.

[0100] Specific examples of the generated base include, but are not limited to, piperidine, 4-hydroxyethylpiperidine, 4-(3-phenylpropylpiperidine), cyclohexylamine, diisopropylamine, dicyclohexylamine, dimethylpiperidine, 2,6-dimethylpiperidine, methylcyclohexylamine, 4-hydroxymethylpiperidine, diisobutylamine, isopropylcyclohexylamine, dis-sec-isobutylamine, etc. Furthermore, these bases may further react with other compounds in the composition to form bases or basic salts having different structures.

[0101] Compound B is preferably a compound represented by any one of the following formulas (1-1), (1-2), and (1-3). [ka] In formulas (1-1) to (1-3), R 1 ~R5 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 1 , two R 2 , the three R's 3 Two or three of the following, two R 4 , or two R 4 One or two of these and R 5 may be bonded to form a ring structure. In formula (1-1), R 1 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group, and each is preferably an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 2 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, or may be a group represented by a combination of these. The above alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. The above alkenyl group may be linear, branched, or cyclic, or may be a group represented by a combination of these. The above alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and more preferably an alkynyl group having 2 to 6 carbon atoms. The above alkynyl group may be linear, branched, or cyclic, or may be a group represented by a combination of these. The aryl group is preferably an aryl group having 1 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and even more preferably a phenyl group. The aryl group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. In formula (1-1), two R 1may be bonded to form a ring structure. The ring structure formed is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The ring structure may be an aliphatic ring structure or an aromatic ring structure, but is preferably an aliphatic ring structure. Specifically, the two R 1 Examples of the ring structure formed by bonding include a piperidine ring which may have a substituent. R 1 As the substituent in the above, any known substituent can be used as long as the effects of the present invention can be obtained, and examples of the substituent include a hydroxy group. Examples of the substituent include an alkyl group, a hydroxyalkyl group, and an aralkyl group. In formula (1-1), R 2 A preferred embodiment of the present invention is R 1 This is similar to the preferred embodiment of the above. Also, two R 2 The ring structure formed by the bonding is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring. The ring structure may be an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure. Examples of the ring structure include a cyclopentanyl group that may have a substituent, a cyclopentenyl group that may have a substituent, and the like. In formula (1-1), n ​​represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably 1 or 2, and particularly preferably 1. In formula (1-1), m represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably 1 or 2, and particularly preferably 1. In formula (1-1), L represents a linking group having a valence of n+m, and is preferably a hydrocarbon group which may have a substituent, and is preferably a saturated hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a group represented by a combination thereof. Furthermore, L may be a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -S-, -C(=O)-, and -S(=O)2-. The above-mentioned saturated hydrocarbon group is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms, and more preferably a saturated hydrocarbon group having 2 to 10 carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 carbon atoms. In particular, when m is 1, n is 1, and L is a divalent linking group, L is preferably an alkylene group, a phenylene group, a naphthylene group, or a group represented by a bond thereof.

[0102] In formula (1-2), R 1 , n, m and L are R in formula (1-1), 1 , n, m and L, and the preferred embodiments are also the same. In formula (1-2), R 3 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group, and each is preferably an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. In formula (1-2), R 3 A preferred embodiment of the present invention is R 2 This is similar to the preferred embodiment of the above. Also, two or three R 3 The ring structure formed by bonding is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring. The ring structure may be an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure. Examples of the ring structure include a cyclopentanyl group that may have a substituent, a cyclopentenyl group that may have a substituent, an adamantyl group, a decahydronaphthyl group, a dicyclopentanyl group, a norbornyl group, and an isobornyl group. Among these, R 3 are each preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

[0103] In formula (1-3), R 1 , n, m and L are R in formula (1-1), 1, n, m and L, and the preferred embodiments are also the same. In formula (1-3), R 4 and R 5 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group, and it is preferable that at least one of them is an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. In formula (1-3), R 4 and R 5 A preferred embodiment of the present invention is R 2 This is similar to the preferred embodiment of the above. In formula (1-3), R 4 and R 5 A preferred embodiment of the present invention is R 2 This is similar to the preferred embodiment of the above. In formula (1-3), two R 4 , or two R 4 One or two of these and R 5 The ring structure formed by bonding with R is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring. 4 One of them and R 5 It is preferred that these rings are bonded to one of the groups represented by the formula (I) to form a tetrahydrofuranyl ring which may be substituted, or a tetrahydropyranyl ring which may be substituted.

[0104] Compound B is also preferably a compound represented by any one of the following formulas (2-1), (2-2), (2-3) and (2-4). [ka] In formulas (2-1) to (2-4), R 6 ~R 11 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 6 , two R 7 ,The three R's 8 Two or three of the following, two R9 , or two R 9 One or two of these and R 10 may be bonded to form a ring structure.

[0105] In formula (2-1), R 6 , R 7 , n and m are R in formula (1-1), 1 , R 2 , n and m have the same meanings, and the preferred embodiments are also the same. In formula (2-1), L represents a linking group having a valence of m+n, and L represents a linking group having a valence of n+m, which is preferably an aliphatic group or an aromatic group which may have a substituent, and is preferably a saturated hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a group represented by a combination thereof. Furthermore, L may be a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -S-, -C(=O)-, and -S(=O)2-. Furthermore, it is preferable that L contains at least an aromatic group, and it is preferable that the m structures in formula (2-1) are directly bonded to the aromatic group contained in L. The above-mentioned saturated hydrocarbon group is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms, and more preferably a saturated hydrocarbon group having 2 to 10 carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 carbon atoms. In particular, when m is 1, n is 1, and L is a divalent linking group, L is preferably an alkylene group, a phenylene group, a naphthylene group, or a group represented by a bond thereof, and more preferably a phenylene group or a group represented by a bond between a phenylene group and an alkylene group.

[0106] In formula (2-2), R 6 , R 8 , n and m are R in formula (1-2), 1 , R3 , n and m have the same meanings, and the preferred embodiments are also the same. In formula (2-2), L has the same meaning as L in formula (2-1), and the preferred embodiments are also the same.

[0107] In formula (2-3), R 6 , R 9 , R 10 , n and m are R in formula (1-3), 1 , R 4 , R 5 , n and m have the same meanings, and the preferred embodiments are also the same. In formula (2-3), L has the same meaning as L in formula (2-1), and the preferred embodiments are also the same.

[0108] In formula (2-4), R 6 , R 11 , n and m are R in formula (1-3), 1 , R 5 , n and m have the same meanings, and the preferred embodiments are also the same. In formula (2-4), L has the same meaning as L in formula (2-1), and the preferred embodiments are also the same.

[0109] Compound B is also preferably a compound represented by any one of the following formulas (3-1), (3-2) and (3-3). [ka] In formulas (3-1) to (3-3), R 12 ~R 16 each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group having a valence of n+m; and two R 12 , two R 13 , two R 13 At least one of and R 14 , the three R's 15 Two or three of the following, two R 16 may be bonded to form a ring structure.

[0110] In formula (3-1), R 12 , R 13 , R 14 , n, m and L are R in formula (1-3), 1 , R 4 , R 5 , n, m and L, and the preferred embodiments are also the same.

[0111] In formula (3-2), R 12 , R 15 , n, m and L are R in formula (1-2), 1 , R 3 , n, m and L, and the preferred embodiments are also the same.

[0112] In formula (3-3), R 12 , R 16 , n, m and L are R in formula (1-1), 1 , R 2 , n, m and L, and the preferred embodiments are also the same.

[0113] It is also preferable to use a compound having no acid group as compound B. According to the above embodiment, migration of metals such as copper is also easily suppressed, and it is considered that the obtained cured film has excellent adhesion.

[0114] The molecular weight of compound B is preferably 200-1,000, more preferably 250-950, and further preferably 300-900.

[0115] Specific examples of compound B include the following compounds. [ka] [ka]

[0116] The content of compound B relative to the total mass of the resin composition of the present invention is preferably from 0.1 to 20.0 mass%, more preferably from 0.5 to 15.0 mass%, and further preferably from 1.0 to 10.0 mass%.

[0117] <Compound C> When the resin composition of the present invention satisfies condition 2, the resin composition of the present invention contains compound C which has a group that generates an acid group by the action of at least one of heat and light and is a compound different from compound B. When the resin composition of the present invention satisfies the condition 1, the resin composition of the present invention may further contain the compound C described above. A compound that falls under compound B is not considered to fall under compound C. Examples of compound C include compounds that have a group that generates an acid group when acted on by at least one of heat and light, but do not have a group that generates a base when acted on by an acid. The group in compound C that generates an acid group when acted upon by at least one of heat and light may be the same as the group in compound B that generates an acid group when acted upon by at least one of heat and light. Specifically, the group in compound C that generates an acid group by the action of at least one of heat and light preferably contains a protected carboxy group, a phenolic hydroxyl group, or a sulfonic acid group. Examples of compound C include known photoacid generators and known thermal acid generators.

[0118] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. The photoacid generator is preferably a photoacid generator that can generate an acid by being exposed to light, either alone or in combination with a sensitizer. Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0119] Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

[0120] Examples of the quinone diazide compound include a monovalent or polyvalent hydroxy compound to which the sulfonic acid of quinone diazide is ester-bonded, a monovalent or polyvalent amino compound to which the sulfonic acid of quinone diazide is sulfonamide-bonded, and a polyhydroxy polyamino compound to which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds do not have 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 a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

[0121] Specific examples of 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 suitable tertiary phenols include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0122] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0123] Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0124] Among these, it is preferable that the quinone diazide compound contains a phenol compound and an ester of 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0125] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, it is possible to obtain a contrast between the exposed and unexposed parts, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0126] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the below-described formula (OS-103), formula (OS-104), or formula (OS-105).

[0127] [ka]

[0128] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. 3 When there are a plurality of X's, they may be the same or different. 3 The alkyl group and alkoxy group in the above formula (X) may have a substituent.3 The alkyl group in the above formula (X) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above formula (I) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, and is 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 or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0129] In formula (OS-1), m3 is 3, and X 3 is a methyl group, and X 3 The substitution position of is the ortho position, and R 34 Particularly preferred are compounds in which R is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group.

[0130] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP2011-209692A and paragraphs 0158 to 0167 of JP2015-194674A, the contents of which are incorporated herein by reference.

[0131] [ka]

[0132] In formula (OS-103) ~ formula (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R may be present in plural. s2 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and may be present in plurality. s6 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 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 following formula may have a known substituent as long as the effects of the present invention can be obtained.

[0133] In formula (OS-103) ~ formula (OS-105), R s2 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. s2 Among R, it is preferable that one or two of them are an alkyl group, an aryl group, or a halogen atom, it is more preferable that one of them is an alkyl group, an aryl group, or a halogen atom, and it is particularly preferable that one of them is an alkyl group and the remaining one is a hydrogen atom. s2 The alkyl group or aryl group represented by the following formula may have a known substituent as long as the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

[0134] In formulae (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1; and when Xs is S, ns is 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 following formula may have a substituent. In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0135] Furthermore, the compound represented by formula (OS-103) above is particularly preferably a compound represented by formula (OS-106), formula (OS-110) or formula (OS-111) below; the compound represented by formula (OS-104) above is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) above is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below. [ka]

[0136] In formula (OS-106) ~ formula (OS-111), R t1 represents an alkyl group, an aryl group, or a heteroaryl group; R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; R t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0137] In formula (OS-106) ~ formula (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0138] In formula (OS-106) ~ formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom. R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the above oxime sulfonate compound, the stereochemical structure (E, Z) of the oxime may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A No. 2011-209692 and paragraphs 0168 to 0194 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference.

[0139] Other preferable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[0140] [ka]

[0141] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. u9 is more preferably a cyano group or an aryl group, u9 More preferably, is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0142] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each 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 amido group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of the rings may be bonded to each other to form a ring. In this case, the rings may be condensed to form a condensed ring together with the benzene ring. u1 ~R u4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and R u1 ~R u4 It is also preferable that at least two of R are bonded to each other to form an aryl group. u1 ~R u4 is preferably a hydrogen atom. Any of the above-mentioned substituents may further have a substituent.

[0143] The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195 to 0207 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, the following 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 Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Chemical Industries, Ltd.).

[0144] Further, compounds represented by the following structural formulas are also preferred examples. [ka]

[0145] Specific examples of the organic halogenated compounds include those described in Wakabayashi et al., Bull Chem. Soc Japan, vol. 42, p. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605 / 1971, JP-A-36281 / 1973, JP-A-32070 / 1980, JP-A-239736 / 1985, JP-A-169835 / 1986, JP-A-169837 / 1987, JP-A-58241 / 1987, JP-A-212401 / 1987, JP-A-70243 / 1988, JP-A-298339 / 1988, and M.P. Hutt, Journal of Heterocyclic Chemistry, vol. 1 (No. 3), (1970), the contents of which are incorporated herein by reference. In particular, preferred examples include oxazole compounds substituted with a trihalomethyl group: S-triazine compounds. More preferably, an s-triazine derivative having at least one mono-, di-, or trihalogen-substituted methyl group 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-triazine, 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-methoxy 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 of the bis(trichloromethyl)-s-triazine 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.

[0146] Examples of the organic borate compounds include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, and Kunz, Martin, "Rad Tech '98. Proceedings of April organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organic boron iodine complexes described in JP-A-6-175554 and JP-A-6-175553; Specific examples include organoboron phosphonium complexes described in JP-A-9-188710, and organoboron transition metal coordination complexes described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, the contents of which are incorporated herein by reference.

[0147] Examples of the disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2001-132318, and diazodisulfone compounds.

[0148] Examples of the onium salt compound include diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and TSBal et al., Polymer, 21, 423 (1980); ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049; phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056; iodine salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; selenonium salts described in JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047(1979); arsonium salts described in C.S.Wen et al., Teh., Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988); and onium salts such as pyridinium salts, the contents of which are incorporated herein by reference.

[0149] The onium salt includes onium salts represented by the following general formulas (RI-I) to (RI-III). [ka] In formula (RI-I), Ar 11Z represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 11 - represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the viewpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. 21 , Ar 22 each independently represents an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group each independently has 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. -represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred. 31 , R 32 , R 33 each independently represents an aryl group, alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, and is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the carbon number of the alkyl group is independently 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the carbon number of the alkyl group is 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

[0150] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0151] When the resin composition contains a photoacid generator, the photoacid generator is used in an amount of preferably 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, even more preferably 0.5 to 10 mass %, still more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.2 mass %, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination in order to impart photosensitivity to a desired light source.

[0152] <Thermal acid generator> The compositions of the present invention may also include a thermal acid generator. The thermal acid generator generates an acid upon heating, and has the effect of promoting the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

[0153] The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select as the thermal acid generator a material that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (cure: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development. The thermal decomposition onset temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C. / min in a pressure-resistant capsule. An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

[0154] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid, etc. Examples of such thermal acid generators include those described in paragraph 0055 of JP2013-072935A.

[0155] Among these, from the viewpoint of being less likely to remain in the organic film and being less likely to deteriorate the physical properties of the organic film, those which generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferred, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, and the like. As the thermal acid generator, preferred are fluorine, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0156] In addition, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as thermal acid generators.

[0157] When the resin composition contains a thermal acid generator, the content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0158] <Compound D> When the resin composition of the present invention satisfies the condition 2, the resin composition of the present invention contains a compound D having a group that generates a base when acted on by an acid. When the resin composition of the present invention satisfies the condition 1, the resin composition of the present invention may further contain the compound D described above. A compound that falls under Compound B is not considered to fall under Compound D. Examples of compound D include compounds that have a group that generates a base when acted on by an acid, but do not have a group that generates an acid group when acted on by at least one of heat and light. Preferred embodiments of the group that generates a base when acted on by an acid in compound D and preferred embodiments of the base generated are the same as the preferred embodiments of the group that generates a base when acted on by an acid in compound B described above and preferred embodiments of the base generated.

[0159] An example of compound D is a compound represented by the following formula (D-1). [ka] In formula (D-1), R 17 each independently represents a hydrogen atom, or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group; n represents an integer of 1 or more; R 18 represents an n-valent organic group. In formula (D-1), R 17is R in the above formula (1-1) 1 The same applies to the preferred embodiments. In formula (D-1), n ​​is preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. In formula (D-1), R 18 is preferably a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -S-, -C(=O)-, and -S(=O)2-. The above-mentioned hydrocarbon group is preferably a saturated hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a group represented by a combination thereof, and more preferably a saturated hydrocarbon group which may have a substituent. The above-mentioned saturated hydrocarbon group is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms, and more preferably a saturated hydrocarbon group having 2 to 10 carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 carbon atoms.

[0160] It is also preferable to use a compound having no acid group as compound D. According to the above embodiment, migration of metals such as copper is also easily suppressed, and it is considered that the obtained cured film has excellent adhesion.

[0161] The molecular weight of compound D is preferably 200-1,000, more preferably 250-950, and further preferably 300-900.

[0162] Specific examples of compound D include the following compounds. [ka]

[0163] The content of compound D relative to the total mass of the resin composition of the present invention is preferably 0.1 to 20.0 mass %, more preferably 0.5 to 15.0 mass %, and further preferably 1.0 to 10.0 mass %.

[0164] <Organometallic complexes> From the viewpoint of chemical resistance, the resin composition of the present invention preferably contains an organometallic complex. The organometallic complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and further preferably a metallocene compound. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives, which may have a substituent, as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom. In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferred that at least two of the organic groups are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, with a hydrocarbon ring being preferred. The five-membered cyclic group is preferably a cyclopentadienyl group. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0165] The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0166] The organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom or may contain two or more types of metal atoms.

[0167] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0168] An embodiment in which the organometallic complex has a photoradical polymerization initiation ability is also one of the preferred embodiments of the present invention. In the present invention, having photoradical polymerization initiation ability means that free radicals capable of initiating radical polymerization can be generated by irradiation with light. For example, when a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation ability can be confirmed by checking whether or not the radical crosslinking agent disappears. To check whether or not the radical crosslinking agent disappears, an appropriate method can be selected depending on the type of radical crosslinking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. When the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[0169] The molecular weight of the organometallic complex is preferably from 50 to 2,000, and more preferably from 100 to 1,000.

[0170] Preferred examples of the organometallic complex include compounds represented by the following formula (P). [ka] In formula (P), M is a metal atom, and each R is independently a substituent. It is preferable that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0171] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom. The aromatic group for R in formula (P) includes aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. The alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. The halogen atom in R includes F, Cl, Br and I. The alkyl group constituting the alkylsulfonyloxy group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. The above R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

[0172] Specific examples of organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds. [ka]

[0173] In addition, compounds described in paragraphs 0078 to 0088 of WO 2018 / 025738 can also be used, but are not limited thereto.

[0174] The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. The organometallic complexes may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0175] <Solvent> The resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0176] 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, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-eth Preferred examples of the cypropionic acid alkyl esters include methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and 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), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0177] Suitable examples of the ethers include 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 dimethyl 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.

[0178] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0179] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0180] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0181] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0182] Preferred examples of the ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0183] 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, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0184] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0185] 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, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more of them, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0186] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

[0187] The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are contained, the total amount thereof is preferably within the above range.

[0188] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat, and particularly preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

[0189] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L mol -1 ·cm -1 It is preferable that the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate as a solvent.

[0190] Any known compound can be used as the photoradical polymerization initiator. For example, 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 oxide, hexaarylbiimidazole, oxime compounds such as 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, organic boron compounds, iron arene complexes, etc. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP Patent No. 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018 / 221177 A, the photopolymerization initiators described in WO 2018 / 110179 A, ​​the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A are mentioned, and the contents of these are also incorporated herein.

[0191] Examples of the ketone compound include the compounds described in paragraph 0087 of JP2015-087611A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0192] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in JP-A-4225898 can be used, the contents of which are incorporated herein by reference.

[0193] Examples of α-hydroxyketone initiators that can be used include 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 (product names: all manufactured by BASF).

[0194] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF).

[0195] As the aminoacetophenone-based initiator, compounds having a maximum absorption wavelength matching a light source having a wavelength of 365 nm or 405 nm, etc., as described in JP-A-2009-191179 can also be used, the contents of which are incorporated herein by reference.

[0196] Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

[0197] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0198] As the photoradical polymerization initiator, more preferably, an oxime compound is used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0199] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP-T-2004-534797 A, compounds described in JP-A-2017-019766 A, compounds described in Japanese Patent No. 6065596 A, compounds described in WO 2015 / 152153 A, compounds described in WO 2017 / 051680 A, compounds described in JP-A-2017-198865 A, compounds described in paragraphs 0025-0038 of WO 2017 / 164127 A, compounds described in WO 2013 / 167515 A, and the like, the contents of which are incorporated herein by reference.

[0200] Preferred oxime compounds include, for example, compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-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 the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0201] [ka]

[0202] Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photoradical polymerization initiator 2 described in JP-A-2012-014052). In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831, and Adeka Arcles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. In addition, DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. In addition, an oxime compound having the following structure can also be used. [ka]

[0203] As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466 and JP-A-06636081, the contents of which are incorporated herein by reference.

[0204] As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0205] In addition, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, paragraph 0345, and compound (C-3) described in JP-A-2013-164471, paragraph 0101, the contents of which are incorporated herein by reference.

[0206] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, the contents of which are incorporated herein. In addition, an example of the oxime compound having a nitro group is Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

[0207] As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0208] As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0209] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1Examples of the electron-withdrawing group of include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and even more preferably an alkoxy group, an alkylsulfanyl group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group.

[0210] The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [ka] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, RX3 ~R X14 each independently represents a hydrogen atom or a substituent; However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0211] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0212] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0213] Most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0214] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal 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 derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0215] More 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. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0216] In addition, the photoradical polymerization initiator may be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketone such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) may be used.

[0217] [ka]

[0218] In formula (I), R I00is 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 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, or a biphenyl group; R I01 is a group represented by formula (II), or R I00 is the same group as R I02 ~R I04 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0219] [ka]

[0220] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as:

[0221] In addition, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0222] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional 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, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in a solvent or the like is improved, so that precipitation is less likely to occur over time, and the stability over time of the resin composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015 / 004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; compounds (C) and (D) described in WO-2016 / 033680; Examples of the photoinitiator include Cmpd1 to 7 described in Japanese Patent Publication No. 34963, the oxime ester photoinitiator described in paragraph 0007 of JP-T-2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, the contents of which are incorporated herein by reference.

[0223] When a photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0224] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like. Examples of the sensitizer include Michler'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-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. 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 (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 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, 3',4'-dimethylacetanilide, and the like. Other sensitizing dyes may also be used. For details about the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of JP2016-027357A, the contents of which are incorporated herein by reference.

[0225] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and further preferably 0.5 to 10 mass%, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more kinds.

[0226] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of the chain transfer agent include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to a low activity radical to generate a radical, or are oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

[0227] In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of WO 2015 / 199219 can also be used, the contents of which are incorporated herein by reference.

[0228] When 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. The chain transfer agent may be one type or two or more types. When two or more types of chain transfer agents are used, the total is preferably within the above range.

[0229] <Base generator> The resin composition of the present invention may contain a base generator (also referred to as "other base generator") different from compound B and compound D. Here, the base generator is a compound capable of generating a base by physical or chemical action. Examples of base generators preferred for the resin composition of the present invention include a thermal base generator and a photobase generator. The base generator does not include the above-mentioned compound B and compound D. The resin composition of the present invention preferably contains a base generator, more preferably contains a thermal base generator or a photobase generator, and further preferably contains a thermal base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package becomes good. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator according to the present invention is not particularly limited, and known base generators can be used.Known base generators include, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, etc. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3). [ka]

[0230] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom. 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3 None of the above has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply to cases in which the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, when the bonded carbon atom forms an amide group together with the nitrogen atom.

[0231] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 At least one of these preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0232] More specifically, Rb 1 and Rb 2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2Rb may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. 1 and Rb 2 is particularly preferably a linear, branched or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0233] Rb 3 Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. 3 may further have a substituent within the range in which the effects of the present invention are exhibited.

[0234] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0235] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as: Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention can be achieved. 13 is preferably an arylalkyl group.

[0236] Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

[0237] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

[0238] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0239] Rb 11 and Rb 12 is Rb in formula (B1-1). 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

[0240] [ka]

[0241] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. N1 and R N2 each independently represents a monovalent organic group.

[0242] In this specification, the term "linking chain" refers to an atomic chain on a path connecting two atoms or atomic groups to be linked, which links these objects with the shortest distance (the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group, 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 the "linking chain length" or "length of the linking chain") is 4. [ka]

[0243] The number of carbon atoms in L in formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, 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 proceeding with the 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 of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0244] The base generator also preferably contains a compound represented by the following formula (N1). [ka]

[0245] In formula (N1), R N1 and R N2 each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0246] L is a divalent linking group, and is 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 present in the atomic sequence that is the shortest path between the two carbonyl groups in the formula.

[0247] In formula (N1), R N1 and R N2 R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. N1 and R N2 When an aliphatic hydrocarbon group is used as the alkyl group, the generated base has high basicity, which is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0248] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the above include a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group. The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The group relating to the combination of the chain alkyl group and the cyclic alkyl group preferably has a carbon number of 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group relating to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an 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. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R N1 and R N2 is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation in which importance is placed on adhesion when laminating with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0249] R N1 and R N2may be linked together to form a cyclic structure. In forming the cyclic structure, an oxygen atom or the like may be included in the chain. N1 and R N2 The cyclic structure formed by may be a single ring or a condensed ring, but is preferably a single ring. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

[0250] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0251] The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and preferably includes a protecting group which is decomposed by an acid.

[0252] Specific examples of the protective group 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 specific examples of such groups include methyloxymethyl (MOM) and ethyloxyethyl (EE). Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0253] The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. It is more 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 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0254] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a linear alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and further 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 carbon atoms, and further preferably 1 to 3 carbon atoms.

[0255] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and still more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, and more preferably has 1 to 4 C═C bonds, and even more preferably has 1 or 2 C═C bonds. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0256] Examples of the base generator include the following, but the present invention is not limited thereto.

[0257] [ka]

[0258] 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.

[0259] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0260] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0261] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0262] The resin composition of the present invention may contain, as a base generator, a compound that generates a base by the action of a base (hereinafter, also referred to as a "base multiplier"). An example of the base amplifier is a compound having a basic group protected by a base-decomposable group. The basic group protected by a base-decomposable group is not particularly limited, and for example, a known amine protecting group that can be deprotected by a base can be used. For example, a group having a carbamate structure is preferable, and examples thereof include a 9-fluorenylmethylcarbamate group, a 1,1-dimethyl-2-cyanomethylcarbamate group, a paranitrobenzylcarbamate group, and a 2,4-dichlorobenzylcarbamate group.

[0263] The base generated from the base amplifier by the action of a base is preferably an amine, more preferably a secondary amine or a tertiary amine. Specific examples of the generated base include, but are not limited to, piperidine, 4-hydroxyethylpiperidine, 4-(3-phenylpropylpiperidine), cyclohexylamine, diisopropylamine, dicyclohexylamine, dimethylpiperidine, 1,3-di-4-piperidylpropane, and the like. Specific examples of the base amplifier include the following compounds. [ka] [ka]

[0264] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and 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, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0265] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

[0266] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond includes a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and the like. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

[0267] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0268] 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.

[0269] Specific examples of the radical crosslinking agent 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 and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. As specific examples, the description in paragraphs 0113 to 0122 of JP2016-027357A can be referred to, and the contents of these are incorporated herein by reference.

[0270] In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of such a compound 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, trimethylolethane, and many other compounds. Examples of the compound include polyfunctional acrylates and methacrylates such as compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the compound, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-A-52-030490, and epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, there can be mentioned polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

[0271] In addition, as preferred radical crosslinking agents other than those described above, compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216, etc., and cardo resins can also be used.

[0272] Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and vinylphosphonic acid compounds described in JP-A-02-025493. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pages 300-308 (1984) can also be used.

[0273] In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015 / 199219 A can also be preferably used, the contents of which are incorporated herein by reference.

[0274] In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) together with specific examples thereof, can also be used as radical crosslinking agents.

[0275] Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

[0276] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligomer types of these may also be used.

[0277] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Corporation; SR-209, 231, and 239, difunctional methacrylates having four ethyleneoxy chains, manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.; and urethane Examples of such oligomers include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmer PME400 (manufactured by NOF Corporation).

[0278] As the radical crosslinking agent, urethane acrylates as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

[0279] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

[0280] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during production and excellent developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0281] From the viewpoints of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for 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, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having urethane bonds, bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as necessary. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, 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, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure. Other examples of the bifunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0282] When the radical crosslinking agent is contained, the content is preferably more than 0% by mass and not more than 60% by mass based on 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.

[0283] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

[0284] [Other crosslinking agents] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in the molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light, such as the above-mentioned photoacid generator, photobase generator, compound B, compound C, etc., and is preferably a compound having, in the molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator, a photobase generator, compound B, compound C, compound D, or the like in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and they may be compounds having the same structure as the compounds produced by the above method.In addition, they may be oligomers formed by self-condensation of the methylol groups of these compounds. As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. 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 glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

[0285] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0286] [ka]

[0287] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0288] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0289] [ka]

[0290] 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 103represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which decomposes under the action of an acid to produce an alkali-soluble group (for example, a group which is eliminated under the action of an acid, -C(R 4 )2COOR 5 A group represented by R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 5 represents a group which is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to produce an alkali-soluble group, a group that is eliminated under the action of an 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 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group 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 may be either 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 cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed 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 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 the preferred embodiments of the alkyl and aryl groups described above. The 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 further have a known substituent within the range in which the effects of the present invention can be obtained.

[0291] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0292] The group which is decomposed by the action of an acid to generate an alkali-soluble group, or the group which is eliminated by the action of an acid, is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0293] Specific examples of compounds having an alkoxymethyl group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds is changed to an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0294] [ka]

[0295] [ka]

[0296] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0297] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0298] Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-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, monoethoxymethylated 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.

[0299] Specific examples of benzoguanamine-based 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, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0300] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably 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''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0301] As the other crosslinking agent, commercially available products may be used, 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. , 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.), Nikalac (registered trademark, the same applies below) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0302] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0303] -Epoxy compounds (compounds having epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200°C or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the resin composition of the present invention at low temperatures and suppressing warping.

[0304] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.

[0305] 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, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-20E, Likaresin (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (all trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, Epolead (registered trademark) GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 (all trade names, manufactured by Daicel CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-300 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, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. The following compounds are also preferably used.

[0306] [ka]

[0307] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0308] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0309] -Oxetane compounds (compounds having an oxetanyl group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

[0310] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0311] Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0312] The content of the other crosslinking agent is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

[0313] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, and the like.

[0314] [Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, compounds described in paragraphs 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0315] [ka]

[0316] 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- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0317] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0318] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

[0319] 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, relative to 100 parts by mass of the specific resin. By making it equal to or more than the lower limit, the adhesion between the pattern and the metal layer becomes good, and by making it equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be of only one type, or of two or more types. When two or more types are used, the total is preferably within the above range.

[0320] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit migration of metal ions originating from the metal layer (metal wiring) into the film.

[0321] The migration inhibitor is not particularly limited, but includes compounds having a heterocycle (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), compounds having thioureas and 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.

[0322] Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.

[0323] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of these compounds are incorporated herein by reference.

[0324] Specific examples of the migration inhibitor include the following compounds.

[0325] [ka]

[0326] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition of the present invention.

[0327] The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, the total amount is preferably within the above range.

[0328] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0329] Specific examples of the polymerization inhibitor 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 cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine 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, dibutyldithiocarbamate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A can also be used, the contents of which are incorporated herein by reference.

[0330] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, based on the total solid content of the resin composition of the present invention.

[0331] The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0332] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger in order to reduce the performance change over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being 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 preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable, and a secondary amine, a tertiary amine, and an ammonium salt are more preferable. Preferred examples of the acid scavenger 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 bond, aniline derivatives having a hydroxyl group and / or an ether bond, etc. When the acid scavenger has an onium structure, it is preferred that the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0333] 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]non-5-ene, and 1,8-diazabicyclo[5,4,0]undeca-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having 2-oxoalkyl groups, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium 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 bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0334] 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-methylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, isobutyl ... ethylhexylamine, 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, and the like.

[0335] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When the composition contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0336] The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

[0337] <Other additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, it is possible to adjust the properties of the film, etc. These components can be found, for example, in the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of US Patent Application Publication No. 2013 / 0034812), and in paragraphs 0101-0104, 0107-0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein. When these additives are incorporated, the total amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.

[0338] [Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0339] By adding a surfactant to the resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid can be improved, and the uniformity of the coating thickness and the liquid saving can be improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and improving the coatability of the surface to be coated. Therefore, a film with a uniform thickness and small thickness unevenness can be more suitably formed.

[0340] Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, and Megafac R30 (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, and Fluorad FC4432 (all manufactured by 3M Corporation). Examples of the fluorine-based surfactant include Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A and the compounds described in paragraphs 0117 to 0132 of JP2011-132503A can also be used, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant. Specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0341] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-based surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in a side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. In addition, examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0342] The fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and liquid saving properties, and also has good solubility in the composition.

[0343] Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), and the like.

[0344] Examples of hydrocarbon surfactants include Paionin A-76, Newkalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, Paionin P-4050-T, and the like (all manufactured by Takemoto Oil Co., Ltd.).

[0345] 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 (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0346] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0347] Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

[0348] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0349] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0350] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0351] 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 mass% based on the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When the higher fatty acid derivative is two or more types, the total is preferably within the above range.

[0352] [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. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. The addition of the thermal radical polymerization initiator can also advance the polymerization reaction of the resin and the polymerizable compound, thereby further improving the solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0353] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0354] When a thermal polymerization initiator is contained, the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, and further preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0355] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0356] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, further preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0357] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0358] Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of triazine-based ultraviolet 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; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-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.

[0359] In the present invention, the above-mentioned various ultraviolet absorbents may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0360] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0361] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability of the resin composition and provide a good curing pattern.Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc. II) Tetraalkoxytitanium 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 tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0362] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0363] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0364] [Antioxidants] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation property of the cured film and the adhesion to the metal material can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Examples of preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the site (ortho position) adjacent to the phenolic hydroxyl group are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as the antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferred. In addition, as the antioxidant, a phosphorus-based antioxidant 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]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant, the contents of which are incorporated herein by reference. In addition, the composition of the present invention may contain a latent antioxidant as necessary. Examples of latent antioxidants include compounds in which the site functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant when heated at 100 to 250° C. or heated at 80 to 200° C. in the presence of an acid / base catalyst, causing the protecting group to be removed.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Laid-Open No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation). Preferred examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

[0365] [ka]

[0366] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0367] The compound represented by formula (3) suppresses the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin, and also suppresses metal oxidation by preventing rust on metal materials.

[0368] Since it can act on resin and metal materials simultaneously, k is preferably an integer of 2 to 4. 7Examples of the group include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, from the viewpoints of solubility in a developer and metal adhesion, it is preferable to have an alkyl ether group or -NH-, and from the viewpoints of interaction with a resin and metal adhesion due to metal complex formation, -NH- is more preferable.

[0369] Examples of the compound represented by general formula (3) include, but are not limited to, the following structures.

[0370] [ka]

[0371] [ka]

[0372] [ka]

[0373] [ka]

[0374] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By making the amount added 0.1 parts by mass or more, it is easy to obtain the effect of improving the elongation characteristics and adhesion to metal materials even in a high-temperature and high-humidity environment, and by making the amount added 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0375] [Anti-aggregation agent] The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

[0376] In the present invention, the anti-aggregating agent may be used alone or in combination of two or more kinds. The composition of the present invention may or may not contain an anti-agglomerating agent. When the composition of the present invention contains an anti-agglomerating agent, the content of the anti-agglomerating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content mass of the composition of the present invention.

[0377] [Phenol compounds] The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of the phenolic compound 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, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0378] In the present invention, the phenolic compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When it does contain a phenolic compound, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0379] [Other polymer compounds] Examples of the other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.

[0380] In the present invention, the other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, the content of the other polymer compounds is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0381] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, and 3,000 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 At rates below 12,000 mm / s, it is difficult to apply the required thickness for an insulating film for rewiring, for example. 2 At above this rate, the condition of the coated surface may deteriorate.

[0382] The amount of acid groups contained in the resin composition of the present invention (also referred to as the "resist acid value") per gram of the composition is preferably 15.0 mgKOH / g or less, and more preferably 10.0 mgKOH / g or less. The lower limit of the amount of the acid groups is not particularly limited, but is preferably 1.0 mgKOH / g or more, and more preferably 1.5 mgKOH / g. The acid group is an acid group having a pKa of 12 or less, such as a carboxy group or a phenolic hydroxy group. The resist acid value is measured, for example, by a titration method using potassium hydroxide.

[0383] <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 the water content is 2.0% or more, the storage stability of the resin composition may be impaired. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0384] The metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass, from the viewpoint of insulation. Metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, the total of these metals is preferably within the above range.

[0385] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials having a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

[0386] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those existing in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0387] A conventionally known container can be used as the container for the resin composition of the present invention. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resins or a bottle with a seven-layer structure made of six types of resins as the container for the purpose of suppressing impurities from being mixed into the raw materials or the resin composition of the present invention. Examples of such containers include the container described in JP 2015-123351 A.

[0388] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The resin composition is preferably cured by heating, and the heating temperature is 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 a film, a rod, a sphere, or a pellet. In the present invention, the cured product is preferably in the form of a film. In addition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance, or internal stress, and imparting a heat dissipation function, by pattern processing of the resin composition. 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 percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

[0389] <Characteristics of the cured resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be poor. The breaking elongation of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[0390] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be a conventionally known method. The mixing can be performed by using a stirring blade, a ball mill, or by rotating the tank itself. The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

[0391] In addition, it is preferable to perform filtration using a filter in order to remove foreign matter such as dust and fine particles in the resin composition of the present invention. The filter pore size may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene). The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection mode, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage may be connected in series. In addition, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be 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, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used. Furthermore, after filtration using a filter, the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.

[0392] (Method of producing the cured product) The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film. Moreover, the method for producing a cured product of the present invention more preferably includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern. It is particularly preferable that the method for producing a cured product of the present invention includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step. The production method of the present invention preferably includes the film forming step and a step of heating the film. Each step will be described in detail below.

[0393] <Film formation process> The resin composition of the present invention can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.

[0394] [Base material] The type of substrate can be appropriately determined depending on the application, and includes, but is not limited to, substrates for semiconductor preparation such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals 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 substrates, and electrode plates of plasma display panels (PDPs). In the present invention, substrates for semiconductor preparation are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. The shape of the substrate is not particularly limited, and may be circular or rectangular. The size of the substrate is, for example, a diameter of 100 to 450 mm, preferably 200 to 450 mm, if it is circular, and, for example, a length of a short side of 100 to 1000 mm, preferably 200 to 700 mm, if it is rectangular. As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

[0395] Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0396] The resin composition of the present invention is preferably applied to a substrate by coating.

[0397] Specific examples of the application method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the film thickness, more preferred are spin coating, slit coating, spray coating, or inkjet methods, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of a desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention. Also, a process may be performed to remove excess film from the edge of the substrate, such as edge bead rinse (EBR) or back rinse. Furthermore, a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

[0398] <Drying process> After the film-forming step (layer-forming step), the above-mentioned film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. Drying may be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0399] <Exposure process> The film may be subjected to an exposure step to selectively expose the film to light. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film. The amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention. For example, the amount of exposure light is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 is preferable, and 200 to 8,000 mJ / cm 2 is more preferred.

[0400] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0401] In terms of the light source, the exposure wavelength may be, for example, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser second harmonic 532nm, third harmonic 355nm, etc. For the resin composition of the present invention, exposure by a high pressure mercury lamp is particularly preferred, and among these, exposure by i-line is preferred. This makes it possible to obtain a particularly high exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.

[0402] <Post-exposure baking process> The film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably from 1 to 12° C. / min, more preferably from 2 to 10° C. / min, and even more preferably from 3 to 10° C. / min, from the temperature at the start of heating to the maximum heating temperature. The rate of temperature rise may be appropriately changed during heating. The heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0403] <Developing process> After exposure, the film may be subjected to a development step in which the film is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern. Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.

[0404] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0405] When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. When TMAH is used, for example, the content of the basic compound in the developer is preferably from 0.01 to 10 mass %, more preferably from 0.1 to 5 mass %, and even more preferably from 0.3 to 3 mass %, based on the total mass of the developer.

[0406] When the developer contains an organic solvent, the organic solvent may be, for example, an ester, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid), ethyl, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (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, etc., and acetoacetate. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0407] When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

[0408] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The content may be 100% by mass.

[0409] The developer may further comprise other components. Examples of other components include known surfactants and known defoamers.

[0410] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times. As a method of supplying the developer in the development process, a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used.

[0411] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0412] In the developing step, after the treatment with the developer, the pattern may be washed (rinsed) with a rinse liquid. Also, a method of supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.

[0413] [Rinse solution] When the developer is an alkaline aqueous solution, the rinse liquid may be, for example, water. When the developer is an organic solvent-containing developer, the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).

[0414] When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate), ethyl butyl methoxyacetate, ... ethyl dimethylacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl, 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, etc., and ethyl Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0415] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0416] When the rinse liquid contains an organic solvent, the rinse liquid preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Alternatively, the rinse liquid may contain 100% by mass of the organic solvent.

[0417] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoamers.

[0418] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid onto the substrate in a puddle, a method of supplying the rinse liquid onto the substrate in a shower, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. As a method of supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps can be used.

[0419] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0420] <Heating process> The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the above development is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0421] The heating step is preferably a step of promoting a cyclization reaction of the polyimide precursor in the pattern by the action of a base generated from the base generator, a base generated from the compound B, or the like due to heating.

[0422] The heating step is preferably performed at a temperature rise rate of 1 to 12° C. / min from the starting temperature to the maximum heating temperature. The temperature rise rate is more preferably 2 to...

Claims

1. A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and satisfying the following condition 1: Condition 1: A resin composition contains compound B having a group that generates an acid group under the action of heat and a group that generates a base under the action of acid, the group in compound B that generates an acid group under the action of heat contains a protected carboxy group, a phenolic hydroxyl group, or a sulfonic acid group, the group in compound B that generates a base under the action of acid is a group containing an amide structure, the amide structure is decomposed by the action of acid to generate an amine, and the group in compound B that generates an acid group under the action of heat is a protected carboxy group, then compound B is a compound represented by any of formulas (1-1) to (1-3). 【Chemistry 1】 In formulas (1-1) to (1-3), R 1 to R 5 each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group; n and m each independently represent an integer of 2 or greater; L represents a linking group having a valence of n+m; and two R 1 s, two R 2 s, two or three of the three R 3 s, two R 4 s, or one or two of the two R 4 s and R 5 may be bonded to form a ring structure.

2. A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and satisfying the following condition 1: Condition 1: A resin composition contains a compound B having a group that generates an acid group by the action of heat and a group that generates a base by the action of an acid, and the group in the compound B that generates an acid group by the action of heat contains a protected carboxy group, a phenolic hydroxyl group, or a sulfonic acid group, the group in the compound B that generates a base by the action of an acid is a group containing an amide structure, and the group in the compound B that generates an acid group by the action of heat is a protected carboxy group, then compound B is a compound represented by any of formulas (1-1) to (1-3). 【Chemistry 2】 In formulas (1-1) to (1-3), R 1 to R 5 each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group; n and m each independently represent an integer of 2 or greater; L represents a linking group having a valence of n+m; and two R 1 s, two R 2 s, two or three of the three R 3 s, two R 4 s, or one or two of the two R 4 s and R 5 may be bonded to form a ring structure.

3. A resin composition described in claim 1 or 2, wherein when the group in compound B that generates an acid group by the action of heat is a protected phenolic hydroxyl group, compound B is a compound represented by any of the following formulas (2-1), (2-2), (2-3) and (2-4). 【Chemistry 3】 In formulas (2-1) to (2-4), R ６ ~R １１ each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; n and m each independently represent an integer of 1 or more; L represents a linking group containing at least an aromatic group and having a valence of n+m; m structures in formulas (2-1) to (2-4) are directly bonded to the aromatic group contained in L; and two R ６ , two R ７ , the three R's ８ Two or three of the two R ９ , or two R ９ One or two of the above and R １０ may be bonded to form a ring structure.

4. A resin composition described in any one of claims 1 to 3, wherein when the group in compound B that generates an acid group by the action of heat is a protected sulfonic acid group, compound B is a compound represented by any one of the following formulas (3-1), (3-2), and (3-3). 【Chemistry 4】 In formulas (3-1) to (3-3), R １２ ~R １６ each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group; each of n and m independently represents an integer of 1 or more; L represents a linking group having a valence of n+m; １２ , two R １３ , two R １３ At least one of and R １４ , the three R's １５ Two or three of the two R １６ may be bonded to form a ring structure.

5. The resin composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator.

6. The resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound.

7. The resin composition according to any one of claims 1 to 6, wherein the amount of acid groups contained in the composition is 1.0 to 15.0 mg KOH / g per 1 g of the resin composition of the present invention.

8. A cured product obtained by curing the resin composition according to any one of claims 1 to 7.

9. A laminate comprising two or more layers made of the cured product according to claim 8, and a metal layer between any two of the layers made of the cured product.

10. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 7 onto a substrate to form a film.

11. The method for producing a cured product according to claim 10, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.

12. The method for producing a cured product according to claim 10 or 11, comprising a heating step of heating the film at 50 to 450°C.

13. A semiconductor device comprising the cured product according to claim 8 or the laminate according to claim 9.

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