Photosensitive resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device

Abstract

The present invention provides a photosensitive resin composition that exhibits excellent adhesion to metal layers. [Solution] A photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and a photopolymerization initiator, wherein the resin has groups capable of photodimerization reaction; a cured product obtained by curing the photosensitive resin composition; a laminate containing the cured product; a method for producing the cured product; and a semiconductor device containing the cured product or the laminate.

Description

[Technical Field]

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

[0002] Polyimide or polyamide-imide is used in a variety of applications due to its excellent heat resistance and insulation properties. While not limited to these applications, examples in semiconductor devices for packaging include its use as an insulating film, encapsulant, or protective film. It is also used as a base film or coverlay for flexible substrates.

[0003] For example, in the applications described above, polyimide or polyamideimide is used in the form of a photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide, polyimide precursor, polyamideimide, and polyamideimide precursor. Such a photosensitive resin composition can be applied to a substrate, for example by coating, to form a resin film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The above polyimide precursor and the above polyamideimide precursor are cyclized, for example by heating, to become polyimide and polyamideimide, respectively, in the cured product. Since photosensitive resin compositions can be applied using known coating methods, they offer excellent manufacturing adaptability, such as a high degree of design freedom in terms of shape, size, and application location of the applied photosensitive resin composition. In addition to the high performance of polyimides, polyamide-imides, etc., the industrial application development of the above-mentioned photosensitive resin compositions is increasingly anticipated due to these excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a liquid crystal alignment agent containing at least two polymers that are reaction products from raw materials including a tetracarboxylic dianhydride and a diamine; the above polymers include a specific polymer (A) and a polymer (B); the raw materials used to synthesize polymer (A) include at least one compound having a photoreactive structure and do not include a specific compound; and the raw materials used to synthesize polymer (B) include at least one specific compound and do not include a compound having a photoreactive structure. Patent Document 2 describes a liquid crystal alignment agent characterized by containing a polymer having a specific structure in its side chain.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] In a cured product obtained by curing a photosensitive resin composition, it is desired to have excellent adhesion to a metal layer.

[0007] An object of the present invention is to provide a photosensitive resin composition from which a cured product having excellent adhesion to a metal can be obtained, a cured product obtained by curing the above photosensitive resin composition, a laminate containing the above cured product, a method for producing the above cured product, and a semiconductor device containing the above cured product or the above laminate.

Means for Solving the Problems

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, It contains a photopolymerization initiator, The above resin has a group capable of photodimerization. Photosensitive resin composition. <2> The above photodimerizable group is a group having a cinnamoyl structure. <1> The photosensitive resin composition described in [reference]. <3> The above resin contains a radical polymerizable group. <1> or <2> The photosensitive resin composition described in [reference]. <4> Compound B having an alkoxysilyl group further comprises <1> ~ <3> A photosensitive resin composition as described in any one of the above. <5> Compound B having the above alkoxysilyl group has at least one group selected from the group consisting of a photodimerizable group and a radical polymerizable group. <4> The photosensitive resin composition described in [reference]. <6> The above compound B having an alkoxysilyl group has an azole group, <4> or <5> The photosensitive resin composition described in [reference]. <7> The compound C further comprises an azole group and at least one group selected from the group consisting of radical polymerizable groups and photodimerizable groups. <1> ~ <6> A photosensitive resin composition as described in any one of the above. <8> The compound D further comprises having an azole group and lacking an alkoxysilyl group, a radical polymerizable group, and a photodimerizable group. <1> ~ <7> A photosensitive resin composition as described in any one of the above. <9> Used for forming interlayer insulating films for redistribution layers, <1> ~ <8> A photosensitive resin composition as described in any one of the above. <10> <1> ~ <9> A cured product obtained by curing a photosensitive resin composition described in any one of the above. <11> <10> A laminate comprising two or more layers made of the cured material described above, with a metal layer between any of the layers made of the cured material. <12> <1> ~ <9> A method for producing a cured product, comprising a film-forming step of applying a photosensitive resin composition described in any one of the above onto a substrate to form a film. <13> The process includes an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern. <12> A method for producing the cured product described above. <14> The development step further includes a second exposure step in which the pattern obtained by the development is exposed to light. <13> A method for producing the cured product described above. <15> The above film includes a heating step of heating it to 50-450°C. <12> ~ <14> A method for producing a cured product as described in any one of the following. <16> <10> The cured product described above or <11> A semiconductor device including the laminate described above. [Effects of the Invention]

[0009] The present invention provides a photosensitive resin composition that yields a cured product with excellent adhesion to metals, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate. [Modes for carrying out the invention]

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

[0011] (Photosensitive resin composition) The photosensitive resin composition of the present invention (hereinafter also simply referred to as "resin composition") comprises at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and a photopolymerization initiator, wherein the resin has groups capable of photodimerization. Hereinafter, at least one resin selected from the group consisting of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors, which has a group capable of photodimerization, will also be referred to as a "specific resin."

[0012] The photosensitive resin composition of the present invention may be a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, but it is preferably a negative-type photosensitive resin composition. A negative-type photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the unexposed parts (non-exposed areas) are removed by a developer. A positive-type photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the exposed portion (exposed area) is removed by a developer.

[0013] The cured product obtained from the photosensitive resin composition of the present invention exhibits excellent adhesion to metals. The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows.

[0014] The photosensitive resin composition of the present invention comprises a resin having a group capable of photodimerization and a photopolymerization initiator. By using such resins, both polymerization by a photopolymerization initiator and dimerization of photodimerizable groups can be utilized for curing through exposure. As a result, strong bonds are formed between the resins, and the resulting cured product exhibits excellent adhesion to metal. In particular, if the resin has polymerizable groups, or if the photosensitive resin composition contains a crosslinking agent as described later, or if re-exposure occurs before, after, or during heat curing after development, the dimerization of photodimerizable groups in the resin is promoted, and the adhesion to the metal is further improved. By utilizing the re-exposure technique described above, it is believed that the above effects can be obtained with both positive and negative film.

[0015] Furthermore, in conventional photosensitive resin compositions containing photopolymerization initiators, curing was sometimes insufficient, particularly on the surface of the film on the air interface side, resulting in poor chemical resistance. This is presumably because polymerization proceeds insufficiently at the air interface due to the influence of oxygen or moisture. However, since the resin contained in the photosensitive resin composition of the present invention has groups that can undergo photodimerization, the photodimerization reaction proceeds on the surface of the film on the air interface side, so the film hardens sufficiently even on the air interface side, and the resulting cured product is expected to have excellent chemical resistance. Because the cured product has excellent chemical resistance, for example, when a photosensitive resin composition containing a solvent is further applied to a cured product made from the photosensitive resin composition of the present invention and cured to produce a laminate, it is believed that the dissolution of the cured product will be suppressed even if the cured product comes into contact with a developer or the photosensitive resin composition. According to the present invention, it is believed that a cured product with excellent chemical resistance can be obtained in which solubility in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, or mixtures of the above polar solvents and alkaline aqueous solutions is suppressed.

[0016] However, Patent Documents 1 and 2 do not describe photosensitive resin compositions containing a resin having a group capable of photodimerization and a photopolymerization initiator.

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

[0018] <Specific resin> The photosensitive resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and having a group capable of photodimerization (specific resin). The photosensitive resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin, and more preferably contains a polyimide precursor.

[0019] [Groups capable of photodimerization] The specific resin may have photodimerizable groups in the main chain or in the side chains, but it is preferable that they be in the side chains. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains. The group capable of photodimerization is not particularly limited, but it is preferable that it is a group capable of dimerization by ultraviolet light. In addition, the group capable of undergoing a photo-dimerization reaction is preferably a group having a cinnamoyl structure, a coumarin structure, a naphthalene structure, or an anthracene structure, and more preferably a group having a cinnamoyl structure.

[0020] In addition, as the group capable of undergoing a photo-dimerization reaction, a group represented by the following formula (P-1) is preferable. [Chemical formula] In formula (P-1), T 1 and T 2 each independently represent a hydrogen atom or a monovalent organic group, j represents 1 or 2, R 1 each independently represent a monovalent organic group or a bonding site with another structure, R 2 each independently represent a monovalent organic group or a bonding site with another structure, i represents an integer of 0 or more, i + j is 6 or less, and when j is 2, the two Ts 1 may be the same or different from each other, and when j is 2, the two Ts 2 may be the same or different from each other, and at least one in the structure contains a bonding site with another structure.

[0021] In formula (P-1), R 1 each independently represent a monovalent organic group or a bonding site with another structure. When R 1 represents a monovalent organic group, a hydrocarbon group is preferable, and an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a biphenyl group is more preferable. The above hydrocarbon group may be substituted with known substituents. Examples of the substituents include a halogen atom, a cyano group, and the like. In formula (P-1), R 2 each independently represent a monovalent organic group or a bonding site with another structure. When R 2 represents a monovalent organic group, R 2The group is preferably a carboxyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, or an arylcarbonyloxy group. The number of carbon atoms in the alkyl group in the alkylcarbonyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group in the alkenylcarbonyloxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4. The alkenyl group may be linear, branched, or cyclic. The aryl group in the arylcarbonyloxy group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. In formula (P-1), T 1 and T 2 Each of these independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a cyano group, or a halogen atom, and more preferably a hydrogen atom. Also, T 1 and T 2 In a manner in which all of them are hydrogen atoms, or T 1 This is a hydrogen atom, T 2 An embodiment in which is a cyano group or a halogen atom is also a preferred embodiment. In formula (P-1), i represents an integer greater than or equal to 0, preferably an integer between 0 and 3, more preferably an integer between 0 and 2, even more preferably 0 or 1, and particularly preferably 0. In formula (P-1), j represents 1 or 2, and is preferably 1.

[0022] The group represented by formula (P-1) preferably contains at least one binding site to another structure, and preferably contains only one binding site to another structure. Also, R 2 Preferably, at least one of them is a bonding site with another structure, R 2 It is more preferable that one of these sites is a bonding site with another structure. Furthermore, in the group represented by formula (P-1), all R 2is a monovalent organic group, R 1 Another preferred embodiment of the present invention is one in which at least one of the elements is a bonding site with another structure.

[0023] Furthermore, the specific resin preferably contains a structure represented by the following formula (P-2) as a structure containing a group capable of photodimerization. [ka] In formula (P-2), T 1 and T 2 Each of these independently represents a hydrogen atom or a monovalent organic group, n represents 0 or 1, j represents 1 or 2, and R 1 Each of these independently represents a monovalent organic group or a bonding site with another structure, R 2 Each of these independently represents a monovalent organic group or a bonding site with another structure, i represents an integer greater than or equal to 0, i+j is less than or equal to 6, and if j is 2, then T is greater than or equal to 2. 1 These may be the same or different, and if j is 2, then T is 2 or greater. 2 The two values ​​of n may be the same or different, and the two values ​​of n may be the same or different. In formula (P-2), T 1 , T 2 , R 1 , R 2 Preferred embodiments of i and j are the same as those preferred embodiments in formula (P-1) described above. In equation (P-3), n is either 0 or 1, with 0 being more preferable.

[0024] [Polymerizable group] Furthermore, it is preferable that the specific resin has polymerizable groups. Examples of polymerizable groups in specific resins include known polymerizable groups such as radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups. As the radical polymerizable group mentioned above, a group having an ethylenically unsaturated bond is preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, as well as (meth)acrylamide groups and (meth)acryloyloxy groups, with (meth)acryloyloxy groups being preferred.

[0025] Among these, it is preferable that the specific resin contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the photosensitive resin composition preferably contains a photoradical polymerization initiator described below as a photopolymerization initiator, more preferably contains a photoradical polymerization initiator described below and a radical crosslinking agent described below as a photopolymerization initiator, and even more preferably contains a photoradical polymerization initiator described below, a radical crosslinking agent described below and a sensitizer described below as a photopolymerization initiator. From such a photosensitive resin composition, for example, a negative-type photosensitive layer is formed. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the photosensitive resin composition preferably contains a photoacid generator as described below. From such a photosensitive resin composition, for example, a chemically amplified positive-type or negative-type photosensitive layer can be formed.

[0026] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2). Formula (2) [ka] In formula (2), A 1 and A 2 Each of these independently represents an oxygen atom or -NH-, and R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0027] Furthermore, the polyimide precursor used in the present invention preferably contains a photodimerizable group in the repeating unit represented by formula (2) above, and R in formula (2) above 115 and R 111 It is more preferable that at least one of them contains a group capable of photodimerization, R 111 It is even more preferable that it contains a group capable of photodimerization. The preferred embodiment of the photodimerizable group is as described above.

[0028] A in equation (2) 1 and A 2 Each of these independently represents either an oxygen atom or -NH-, with the oxygen atom being preferred. R in equation (2) 111 -Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, 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 two or more of the above. The preferred ranges for these are as described above.

[0029] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0030] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0031] Diamines specifically 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 isophoronediamines; 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'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine , bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0032] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0033] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0034] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0035] Also, R 111From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0036] Also, R 111 The structure may include a group capable of photodimerization. Preferred embodiments of the photodimerization group are as described above. For example, R 111 This structure can also be derived from a diamine compound having a group capable of photodimerization. R 111 If it contains a group capable of photodimerization, R 111 Preferably, the structure includes an aromatic hydrocarbon group and a group containing the photodimerizable group directly bonded to the aromatic hydrocarbon group. The above-mentioned aromatic hydrocarbon group is not particularly limited, but a benzene ring structure is preferred.

[0037] Also, R 111 If it contains a group capable of the above photodimerization reaction, R 111 It is preferable that the structure is represented by the following formula (LD-1). [ka] In formula (LD-1), Y D1 This represents an n+2 valent group containing an aromatic hydrocarbon group, P D1 represents a group having a photodimerizable group, n represents an integer of 1 or more, and * represents R in equation (2). 111 This indicates the bonding site with the nitrogen atom to which it is bonded.

[0038] -Y D1 - In formula (LD-1), Y D1 This represents an n+2 valent group containing an aromatic hydrocarbon group. Y D1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, even more preferably a group from which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group from which three or more hydrogen atoms have been removed from a benzene ring. In formula (LD-1), Y D1 In this case, it is preferable that the bonding sites with the two *s in formula (LD-1) are both aromatic hydrocarbon groups. That is, the two *s in formula (1-1) are Y 1 It is preferable that the aromatic hydrocarbon ring structure contained in it be directly bonded. Also, in equation (LD-1), Y D1 In P D1The binding sites with are preferably all aromatic hydrocarbon groups. That is, P D1 is preferably directly bonded to the aromatic hydrocarbon ring structure contained in Y D1 .

[0039] Y D1 preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and more preferably is at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5).

Chemical formula

[0040] Among these, from the viewpoint of solvent solubility, Y 1 preferably contains a structure represented by any one of Formula (A2-1) to Formula (A2-4), and more preferably contains a structure represented by either Formula (A2-1) or Formula (A2-4).

[0041] In Formula (A2-1) to (A2-5), R A211 ~R A214 、R A221 ~R A224 、R A231 ~R A238 、R A241 ~R A248 and R A251 ~R A258 do not include the bonding site with the carbonyl group in the above Formula (1-1), and at least one of R A211 ~R A214 , at least one of R A221 ~R A224 , at least one of R A231 ~R A238 , at least one of R A241 ~R A248 , and at least one of R A251 ~R A258 may be the bonding site with P D1 in the above Formula (LD-1). In Formula (A2-1), when R A211 ~R A214 is not the bonding site with P D1 , R A211 ~R A214 each independently preferably represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable. The above R A211 ~R A214Examples of halogen atoms in the above-mentioned halogenated alkyl group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with chlorine atoms or bromine atoms being preferred. In formula (A2-2), R A221 ~R A224 R in equation (A2-1) A211 ~R A214 These are synonymous, and the same applies to the preferred form. In formula (A2-3), R A231 ~R A238 Each of these elements can independently represent a hydrogen atom, a C1-C6 alkyl group, a C3-C12 cyclic alkyl group, a C1-C6 alkoxy group, a hydroxyl group, a cyano group, a C1-C3 halogenated alkyl group, or a halogen atom. From the viewpoint of solvent solubility, a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C1-C3 halogenated alkyl group are more preferred, and a hydrogen atom or a C1-C6 alkyl group are even more preferred. The above R A231 ~R A238 Examples of halogen atoms in the above-mentioned halogenated alkyl group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with chlorine atoms or bromine atoms being preferred. In formula (A2-3), L A231 These include single bonds, divalent saturated hydrocarbon groups with 1 to 6 carbon atoms, divalent unsaturated hydrocarbon groups with 5 to 24 carbon atoms, and -O-, -S-, -NR groups. N - Preferably represents a heterocyclic group or a halogenated alkylene group having 1 to 6 carbon atoms, a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and more preferably a single bond or -O-. The above R N represents a hydrogen atom or a hydrocarbon group, with a hydrogen atom, an alkyl group, or an aryl group being more preferred, a hydrogen atom or an alkyl group being even more preferred, and a hydrogen atom being particularly preferred. The above-mentioned divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but it is preferable that it be a divalent aromatic hydrocarbon group. The above heterocyclic groups are preferably, for example, groups obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring, and more preferably groups obtained by removing two hydrogen atoms from ring structures such as a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, and morpholine ring. These heterocyclic rings may further form fused rings with other heterocyclic rings or hydrocarbon rings. The number of ring members in the above heterocycle is preferably 5 to 10, and more preferably 5 or 6. Furthermore, the heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of halogen atoms in the above-mentioned halogenated alkylene group include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms or bromine atoms being preferred. In formula (A2-4), R A241 ~R A248 , L A241 R in equation (A2-3) A231 ~R A238 , L A231 These are synonymous, and the same applies to the preferred form. In formula (A2-5), R A251 ~R A258 R in equation (A2-1) A211 ~R A214 These are synonymous, and the same applies to the preferred form.

[0042] In formula (A2-1), R A211 ~R A214 At least one of them is P in equation (LD-1) D1 It is preferable that this is a bonding site with R A211 ~R A214 One of them is the above P D1 It is more preferable that the bonding site is with R A213 P D1 It is preferable that this is a bonding site with the In formula (A2-2), R A221 ~R A224At least one of them is P in equation (LD-1) D1 It is preferable that this is a bonding site with R A221 ~R A224 One of them is the above P D1 It is more preferable that the bonding site is with R A223 P D1 It is preferable that this is a bonding site with the In formula (A2-3), R A231 ~R A238 At least one of them is P in equation (LD-1) D1 It is preferable that this is a bonding site with R A231 ~R A238 Two of them are the above P D1 It is more preferable that the bonding site is with R A231 ~R A234 One of the following, R A235 ~R A238 One of the above two is P D1 It is even more preferable that the bonding site is with R A231 and R A238 The two above are P D1 It is particularly preferable that this is a bonding site with [the other site]. In formula (A2-4), R A241 ~R A248 At least one of them is P in equation (LD-1) D1 It is preferable that this is a bonding site with R A241 ~R A248 Two of them are the above P D1 It is more preferable that the bonding site is with R A241 ~R A244 One of the following, R A245 ~R A248 One of the above two is P D1 It is even more preferable that the bonding site is with R A241 and R A248 The two above are P D1 It is particularly preferable that this is a bonding site with [the other site]. In formula (A2-5), R A251 ~R A258 At least one of them is P in equation (LD-1) D1 It is preferable that this is a bonding site with R A251 ~RA258 Two of them are the above P D1 It is more preferable that the bonding site is with R A251 ~R A254 One of the following, R A255 ~R A258 One of the above two is P D1 It is even more preferable that the bonding site is with R A253 and R A257 The two above are P D1 It is particularly preferable that this is a bonding site with [the other site].

[0043] In equations (A2-1) to (A2-5), the two *s are preferably the *s in equation (LD-1). That is, the R in equation (2). 111 The two nitrogen atoms to which it is bonded are preferably directly bonded to the positions represented by the two * symbols in formulas (A2-1) to (A2-5).

[0044] Among these, Y D1 It is preferable that the group is represented by the following formula (Y-1) or (Y-2). [ka] In formula (Y-1), R Y11 , R Y12 , R Y13 These are R in equation (A2-1), respectively. A211 , R A212 and R A214 This is synonymous with the same as the preferred configuration. In formula (Y-2), R Y21 ~R Y26 These are R in equation (A2-4), respectively. A242 ~R A247 This is synonymous with the same as the preferred configuration. In equation (Y-1) or equation (Y-2), * represents R in equation (2), respectively. 111 The # indicates the bonding sites with the two nitrogen atoms to which it is bonded, and each of these is represented by P in formula (LD-1). D1 The connection sites are shown for each.

[0045] -P D1 - In formula (LD-1), P D1 This represents a group having a photodimerizable group. The preferred embodiment of the photodimerizable group is the same as the preferred embodiment of the photodimerizable group in the specific resin described above. PD1 is preferably a group represented by the following formula (PD-1). [ka] In formula (PD-1), L PD1 represents a single bond or an m+1 valent linking group, X PD1 * represents a group capable of photodimerization, m represents an integer greater than or equal to 1, and * represents Y in formula (LD-1). D1 This represents the connection point.

[0046] In formula (PD-1), L PD1 is a single bond, or a hydrocarbon group, ether bond, carbonyl group, thioether bond, sulfonyl group, -NR N - or groups in which two or more of these are bonded together are preferred, and these may be single bonds, hydrocarbon groups, ether bonds, carbonyl groups, -NR N -, or a group in which two or more of these are bonded together is more preferable. The above R N represents a hydrogen atom or a hydrocarbon group, with a hydrogen atom, an alkyl group, or an aryl group being more preferred, a hydrogen atom or an alkyl group being even more preferred, and a hydrogen atom being particularly preferred. The above L PD1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination thereof. More preferably, it is a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing 2 or more hydrogen atoms from a benzene ring, or a group represented by a combination thereof.

[0047] In formula (PD-1), X PD1 The preferred embodiment is the same as the preferred embodiment of the photodimerizable group in the specified resin described above.

[0048] In formula (PD-1), m is preferably an integer between 1 and 4, more preferably 1 or 2, and particularly preferably 1.

[0049] -n- In formula (LD-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0050] The structure represented by the above formula (LD-1) can be obtained, for example, as a structure derived from a diamine represented by the following formula (LDA-1). [ka] In the above formula (LDA-1), Y D1 , P D1 n and n are the same as Y in the above equation (LD-1). D1 , P D1 It is synonymous with n, and the preferred form is similar.

[0051] Also, R 111 The structure may include polymerizable groups. For example, R 111 This structure can also be derived from a diamine compound having a polymerizable group. The diamine compound having a polymerizable group is not particularly limited, but it is preferably a compound containing an aromatic ring structure, and more preferably a compound having a structure in which an amino group and a polymerizable group are directly attached to the aromatic ring structure. Preferred polymerizable groups include groups containing ethylenically unsaturated bonds, cyclic ether groups, methylol groups, or alkoxymethyl groups; more preferably vinyl groups, (meth)allyl groups, (meth)acrylamide groups, (meth)acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups, or alkoxymethyl groups; and even more preferably (meth)acryloxy groups, (meth)acrylamide groups, epoxy groups, methylol groups, or alkoxymethyl groups.

[0052] Also, R 111If the structure contains polymerizable groups, 111 It is preferable that the structure is represented by the following formula (1-1). [ka] In formula (1-1), Y 1 This represents an n+2 valent group containing an aromatic hydrocarbon group, P 1 * represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents R in formula (2). 111 This indicates the bonding site with the nitrogen atom to which it is bonded.

[0053] -Y 1 - In formula (1-1), Y 1 This represents an n+2 valent group containing an aromatic hydrocarbon group. Y 1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, even more preferably a group from which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group from which three or more hydrogen atoms have been removed from a benzene ring. In formula (1-1), Y 1 In this, it is preferable that the bonding sites with the two *s in formula (1-1) are both aromatic hydrocarbon groups. That is, the two *s in formula (1-1) are Y 1 It is preferable that the aromatic hydrocarbon ring structure contained in it be directly bonded. Also, in equation (1-1), Y 1 In P 1 The bonding sites are preferably aromatic hydrocarbon groups. That is, P 1 Y 1 It is preferable that the aromatic hydrocarbon ring structure contained in it be directly bonded.

[0054] Y 1It is preferable that it includes at least one structure selected from the group consisting of structures represented by the above formulas (A2-1) to (A2-5), and more preferably at least one structure selected from the group consisting of structures represented by the above formulas (A2-1) to (A2-5). However, in the explanation of equations (A2-1) to (A2-5) above, "P in equation (LD-1)" D1 The description "the bonding site with P in formula (1-1)" is "P 1 This should be interpreted as "the connection point with." Also, Y 1 A preferred embodiment is Y in formula (LD-1). D1 This is similar to the preferred embodiment.

[0055] -P 1 - In formula (1-1), P 1 This represents a group containing a polymerizable group. Preferred polymerizable groups include groups containing ethylenically unsaturated bonds, cyclic ether groups, methylol groups, or alkoxymethyl groups; more preferably vinyl groups, (meth)allyl groups, (meth)acrylamide groups, (meth)acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups, or alkoxymethyl groups; and even more preferably (meth)acryloxy groups, (meth)acrylamide groups, epoxy groups, methylol groups, or alkoxymethyl groups. P 1 The number of polymerizable groups contained in is one or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0056] Also, P 1 Preferably, the group is represented by the following formula (P-1). [ka] In formula (P-1), L 1 represents a single bond or an m+1 valent linking group, A 2* represents a polymerizable group, m represents an integer greater than or equal to 1, and * represents Y 1 This represents the connection point. In formula (P-1), L 1 is a single bond, or a hydrocarbon group, ether bond, carbonyl group, thioether bond, sulfonyl group, -NR N - or groups in which two or more of these are bonded together are preferred, and these may be single bonds, hydrocarbon groups, ether bonds, carbonyl groups, -NR N -, or a group in which two or more of these are bonded together is more preferable. The above R N This is as stated above. The above L 1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination thereof. More preferably, it is a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing 2 or more hydrogen atoms from a benzene ring, or a group represented by a combination thereof.

[0057] In formula (P-1), A 2 The group is preferably a vinyl group, (meth)allyl group, (meth)acrylamide group, (meth)acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, methylol group, or alkoxymethyl group, and more preferably a (meth)acryloxy group, (meth)acrylamide group, epoxy group, methylol group, or alkoxymethyl group.

[0058] In formula (P-1), m is preferably an integer between 1 and 15, more preferably an integer between 1 and 10, even more preferably an integer between 1 and 5, particularly preferably 1 or 2, and most preferably 1.

[0059] Also, P 1 It is preferable that the group is represented by the following formula (P-2) or formula (P-3). [ka] In formula (P-2), A 2 * represents a polymerizable group, and * represents Y 1This represents the connection point. In formula (P-2), A 2 A in equation (P-1) 2 This is synonymous with the same as the preferred configuration. In formula (P-3), A 2 represents a polymerizable group, L 2 This refers to a hydrocarbon group, or a hydrocarbon group and an ether bond, carbonyl group, thioether bond, sulfonyl group, -NR N -, or represents a group formed by the bonding of two or more of these, Z 1 * represents an ether bond, ester bond, urethane bond, urea bond, amide bond, or carbonate bond, and * represents Y 1 This represents the bonding site with R. N This is as stated above. In formula (P-3), A 2 A in equation (P-1) 2 This is synonymous with the same as the preferred configuration. In formula (P-3), L 2 The group is preferably a hydrocarbon group, a (poly)alkylene oxy group, or a combination thereof. The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a combination thereof, and more preferably an alkylene group. In this specification, (poly)alkyleneoxy group means alkyleneoxy group or polyalkyleneoxy group. In the present invention, polyalkyleneoxy group means 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. If the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be random, have blocks, or have patterns such as alternating arrangements. The alkylene group described above is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, even more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. In the above (poly)alkylene oxy group, an alkylene group having 2 to 10 carbon atoms is preferred, an alkylene group having 2 to 4 carbon atoms is more preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is even more preferred. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2 to 4. In formula (P-3), Z 1 represents an ether bond, ester bond, urethane bond, urea bond, amide bond, or carbonate bond, with ester bonds, urethane bonds, urea bonds, or amide bonds being more preferred. In the present invention, when terms such as "ester bond," "urethane bond," and "amide bond" are used, the orientation of these bonds is not limited. For example, the above Z 1 If the bond is an ester bond, then Z 1 L in 2 The bonding site may be a carbon atom in the ester bond, or it may be an oxygen atom.

[0060] -n- In formula (1-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0061] R in equation (2) 115 represents a tetravalent organic group. Preferably, the tetravalent organic group is one containing an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents a bonding site with another structure. [ka] In formula (5), R 112 The linking group is a single bond or a divalent linking group, preferably a single bond or a group selected from a C1-C10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO2-, and -NHCO-, which may be substituted with a fluorine atom, and combinations thereof; more preferably a group selected from a single bond or a C1-C3 alkylene group, -O-, -CO-, -S-, and -SO2-, which may be substituted with a fluorine atom; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0062] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R 115 The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in equation (2) is 115 This is synonymous with the same thing, and the preferred range is also similar.

[0063] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

[0064] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0065] In equation (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 Examples include residues of bisaminophenol derivatives.

[0066] R in equation (2) 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R 113 and R 114 It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having ethylenically unsaturated bonds are preferred. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0067] [ka]

[0068] In equation (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In equation (III), * represents a bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the above-mentioned group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

[0069] In equation (2), R 113 If R is a hydrogen atom, 114 If the atom is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0070] In equation (2), R 113 and R 114 At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group are preferred.

[0071] Furthermore, the polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0072] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0073] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to broaden the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, R 111 and R 112 Each of these independently represents a divalent organic group, R 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0074] A 1 , A 2 , R 111 , R 113 and R 114 These are, independently of A in equation (2), 1 , A 2 , R 111 , R 113 and R114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) 112 This is synonymous with the same thing, and the preferred range is also similar.

[0075] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0076] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0077] 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 degree of molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, if the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0078] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains.

[0079] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. Fluorine atoms are, for example, R132 in the repeating unit represented by formula (4) described later, or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit represented by formula (4) described later, R132 in the repeating unit represented by formula (4) described later, or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0080] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 131 It is more preferable that it be included as an organically modified (poly)siloxane structure, as described later. Furthermore, the silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0081] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later.131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0082] [ka]

[0083] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0084] In formula (IV), R 21 This represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof. Of the alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0085] Among these, R 21 It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). 21 This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in L are as described above for R 21 This is similar to the preferred embodiment of the alkylene group having 2 to 12 carbon atoms, or the (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In equations (R1) to (R3), * is equivalent to * in equation (IV), and the same applies to the preferred embodiment. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0086] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0087] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0088] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds. Polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having an ethylenically unsaturated bond include, for example, R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0089] -Polar Conversion Group- Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. 131 , R 132 It is found at the ends of polyimides, etc.

[0090] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​shall be those calculated using ACD / ChemSketch®. Alternatively, values ​​published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to. Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. The polyimide preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0091] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0092] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, R 132 This represents a tetravalent organic group. If it has polymerizable groups, the polymerizable groups are R 131 and R 132 It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups are equivalent to formula (4). Formula (4-2) [ka] R 134 and R 135 At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0093] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. R 131 R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is 111 Similar examples are given, and the preferred range is also similar. Also, R 131 Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. 111 Examples include:

[0094] R 131 It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine that does not contain an aromatic ring.

[0095] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0096] R 132 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is 115 Similar examples are given, and the preferred range is also similar. For example, R 115 The four bonds of the tetravalent organic group, as exemplified above, bond with the four -C(=O)- parts in formula (4) above to form a fused ring.

[0097] Also, R 132 Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. 115 Examples include: From the standpoint of the strength of the organic film, R 132 It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0098] R131 and R 132 It is also preferable that at least one of them has an OH group. More specifically, R 131 As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R 132 As such, (DAA-1) to (DAA-5) above can be cited as more preferable examples.

[0099] Furthermore, it is preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

[0100] Furthermore, to improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0101] Furthermore, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-captives such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0102] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was found at 1377 cm⁻¹. -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0103] Polyimides are all of the same type R 131 or R 132 It may include the repeating unit represented by the above formula (4), and may include two or more different types of R 131 or R 132 The polyimide may also contain repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (2).

[0104] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0105] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit set for the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[0106] [Polyamide-imide precursors] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group. Furthermore, the polyamide-imide precursor is R 111 It is preferable that the group has a group capable of photodimerization.

[0107] In formula (PAI-2), R 117 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0108] Also, R 117 It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the above tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used individually or in combination of two or more.

[0109] Specifically, preferred tricarboxylic acid compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0110] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene group. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

[0111] In formula (PAI-2), R 111 , A 2 , R 113 These are the R values ​​in equation (2) above. 111 , A 2 , R 113 This is synonymous with the same as the preferred configuration.

[0112] The polyamide-imide precursor may further contain other repeating units. Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below. [ka]

[0113] In formula (PAI-1), R 116 represents a divalent organic group, R111 This represents a divalent organic group. In formula (PAI-1), R 116 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0114] Also, R 116It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

[0115] Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0116] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebaic acid, and hexadeca. Examples include fluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

[0117] In formula (PAI-1), R 111 R in equation (2) above is 111 This is synonymous with the same as the preferred configuration.

[0118] Furthermore, the polyamide-imide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0119] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine component.

[0120] One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2). Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0121] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of dispersion of the molecular weight of the polyamide-imide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imide precursors are treated as a single resin are, respectively, within the above ranges.

[0122] [Polyamide-imide] The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide, or a polyamide-imide that is soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyamide-imide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in its main chain.

[0123] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamide-imide contains fluorine atoms. Fluorine atoms, for example, are R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later.117 , or R 111 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0124] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamide-imide may have ethylenically unsaturated bonds. Polyamide-imides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as a group having an ethylenically unsaturated bond. A preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

[0125] The amount of ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0126] -Polymerizable groups other than ethylenically unsaturated bonds- Polyamide-imides may have polymerizable groups other than ethylenically unsaturated bonds. Polymerizable groups other than ethylenically unsaturated bonds in polyamide-imides include the same groups as those described above for polymerizable groups other than ethylenically unsaturated bonds in polyimides. Polymerizable groups other than ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (PAI-3) described later.111 It is preferable that it be included in The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0127] -Polar Conversion Group- Polyamide-imides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyamide-imides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same.

[0128] - Acid Value - When polyamide-imide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamide-imide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyamide-imide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, examples of acid groups contained in polyamideimides include the same groups as those in the polyimides described above, and the preferred embodiments are also the same.

[0129] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyamide-imide has a phenolic hydroxyl group. Polyamide-imides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. Phenolic hydroxyl groups are, for example, R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0130] The polyamide-imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 These are the R values ​​in equation (PAI-2), respectively. 111 and R 117 This is synonymous with the same as the preferred configuration. If it has polymerizable groups, the polymerizable groups are R 111 and R 117 It may be located at least one of the two or at the end of the polyamide-imide.

[0131] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to encapsulate the main chain ends of the polyamide-imide with an end-capturing agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. The preferred embodiment of the end-capturing agent is the same as the preferred embodiment of the end-capturing agent in polyimide described above.

[0132] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of polyamide-imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

[0133] Polyamide-imide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R111 or R117, and may contain two or more different types of R 131 or R 132 The polyamide-imide may also contain repeating units represented by the above formula (PAI-3). In addition to the repeating units represented by the above formula (PAI-3), the polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0134] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and then completely imidizing it using a known imidation reaction method, or by stopping the imidation reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with its polyamide-imide precursor to introduce a partial imide structure.

[0135] The weight-average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of molecular weight dispersion of the polyamide-imide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of molecular weight dispersion of the polyamide-imide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imides are treated as a single resin are, respectively, within the above ranges.

[0136] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0137] -End-capturing agent- In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, examples of end encapsulants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the standpoint of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred 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 phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants. Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0138] -Solid precipitation- The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[0139] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin or may contain two or more specific resins. When it contains two or more specific resins, it is preferable that the total amount is within the above range.

[0140] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above). 115 Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0141] <Other resins> The resin composition of the present invention may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -3 By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0142] If the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0143] <Compounds containing an alkoxysilyl group> The photosensitive resin composition of the present invention preferably contains compound B, which is a compound having an alkoxysilyl group. Compounds that fall under the category of the specified resin mentioned above are not considered to be compound B.

[0144] [Alkoxysilyl group] The alkoxysilyl group may be a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group, but from the viewpoint of pattern formation and adhesion of the cured product to the metal, a trialkoxysilyl group is preferred. The alkoxy group in the above-mentioned alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably an ethoxy group.

[0145] [Groups capable of photodimerization] Compound B preferably has at least one group selected from the group consisting of a photodimerizable group and a radical polymerizable group, and more preferably has at least one group selected from the group consisting of a cinnamoyl structure and a radical polymerizable group. The preferred embodiment of the photodimerizable group contained in compound B is the same as the preferred embodiment of the photodimerizable group contained in the specific resin described above. Furthermore, as the radical polymerizable group contained in compound B, a group having an ethylenically unsaturated bond is preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, as well as (meth)acrylamide groups and (meth)acryloyloxy groups, with (meth)acryloyloxy groups being preferred.

[0146] [Formula (B1-1), Formula (B1-2)] Compound B is preferably a compound represented by the following formula (B1-1) or formula (B1-2). Furthermore, it is preferable that the compound represented by the following formula (B1-1) or formula (B1-2) is a compound corresponding to the low molecular weight compound B described later. [ka] In formula (B1-1), R 1 Each of these independently represents a monovalent organic group, n represents an integer from 0 to 5, and T 1 and T 2 Each of these independently represents a hydrogen atom or a monovalent organic group, and X 1 represents a divalent linking group, Z 1 This represents an alkoxysilyl group. In formula (B1-2), R 1 Each of these independently represents a monovalent organic group, m represents an integer from 0 to 4, and T 3 ~T 6 Each of these independently represents a hydrogen atom or a monovalent organic group, and X 2 and X 3 Each of these independently represents a divalent linking group, Z 2 and Z 3 Each of these independently represents an alkoxysilyl group.

[0147] In formula (B1-1), R 1 Each of these independently represents a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferred. 1 When represents a monovalent organic group, a hydrocarbon group is preferred, and an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a biphenyl group is more preferred. The above hydrocarbon group may be substituted with known substituents. Examples of substituents include halogen atoms and cyano groups. In formula (B1-1), n ​​represents an integer between 0 and 5, preferably between 0 and 3, more preferably 0 or 1, and particularly preferably 0. Also, if n is 1, R 1 is T 1 It is preferable that it is located in the para position relative to the bonded carbon atom. In formula (B1-1), T 1 and T 2 Each of these independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a cyano group, or a halogen atom, and more preferably a hydrogen atom. Also, T 1 and T 2 In a manner in which all of them are hydrogen atoms, or T1 This is a hydrogen atom, T 2 An embodiment in which is a cyano group or a halogen atom is also a preferred embodiment. In formula (B1-1), X 1 The symbol represents a divalent linking group, which is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N - Preferably a group represented by bonding with at least one group selected from the group consisting of -. The above R N represents a hydrogen atom or a hydrocarbon group, with a hydrogen atom, an alkyl group, or an aryl group being more preferred, a hydrogen atom or an alkyl group being even more preferred, and a hydrogen atom being particularly preferred. Also, X 1 An embodiment in which the base is represented by the following formula (X-1) is also one of the preferred embodiments. [ka] In formula (X-1), L X1 represents a single bond or a divalent linking group, A X is -O- or -NR N - represents L X2 represents a divalent linking group, and * represents T in formula (B1-1). 1 The symbol represents the bonding site with the bonded carbon atom, and # is Z in formula (B1-1). 1 This represents the connection point. The above R N This is as stated above. In formula (X-1), L X1 It is preferably a single bond or a hydrocarbon group, more preferably a single bond or an optionally substituted ethylene group, and even more preferably a single bond or an unsubstituted ethylene group. Examples of substituents on the ethylene group include cyano groups and halogen atoms. In formula (X-1), A X -NR N - is preferred, and -NH- is more preferred. In formula (X-1), L X2 These are hydrocarbon groups, or hydrocarbon groups with -O-, -S-, -C(=O)-, -S(=O)2- and -NR NA group represented by bonding with at least one group selected from the group consisting of - is preferred, a hydrocarbon group is more preferred, and an alkylene group is even more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 3 to 6. In formula (B1-1), Z 1 The preferred embodiment is the same as the preferred embodiment of the alkoxysilyl group in compound B described above.

[0148] In formula (B1-2), R 1 A preferred embodiment is R of formula (B1-1). 1 This is similar to the preferred embodiment. In formula (B1-2), T 3 ~T 6 Each of these independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a cyano group, or a halogen atom, and more preferably a hydrogen atom. Also, T 1 and T 2 In a manner in which all of them are hydrogen atoms, or T 4 and T 5 This is a hydrogen atom, T 3 and T 6 An embodiment in which is a cyano group or a halogen atom is also a preferred embodiment. In formula (B1-2), X 2 and X 3 Each of these independently represents a divalent linking group, which is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N - Preferably a group represented by bonding with at least one group selected from the group consisting of -. The above R N This is as stated above. In formula (B1-2), X 2 and X 3 A preferred embodiment is one in which one or both of the elements are groups represented by the above formula (X-1). However, X 2 If is the base represented by the above formula (X-1), then the * in formula (X-1) is the same as the T in formula (B1-2). 3The symbol represents the bonding site with the bonded carbon atom, and # is the Z in equation (1-2). 2 This represents the connection point. Also, X 3 If is the base represented by the above formula (X-1), then the * in formula (X-1) is the same as the T in formula (B1-2). 6 The symbol represents the bonding site with the bonded carbon atom, and # is Z in formula (B1-2). 3 This represents the connection point. In formula (B1-2), Z 2 and Z 3 The preferred embodiments are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0149] [Azole group] Furthermore, compound B may also preferably have an azole group. According to the above embodiment, it is believed that the adhesion of the cured product to the metal is further improved by the coordination of the azole group with a metal such as copper. The azole group in compound B may be a heterogeneous five-membered ring compound containing one or more nitrogen atoms as ring members, and may have substituents or a fused ring structure, from which one or more hydrogen atoms have been removed. However, it is preferable that the group be a heterogeneous five-membered ring compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members, and may have substituents, from which one or more hydrogen atoms have been removed. From the viewpoint of adhesion of the cured product to the metal, the azole group is preferably a group having a structure in which one or more hydrogen atoms have been removed from a pyrrole ring, pyrazole ring, indazole ring, imidazole ring, benzimidazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, benzotriazole ring, or tetrazole ring, and more preferably a group having a structure in which one or more hydrogen atoms have been removed from an imidazole ring, benzimidazole ring, 1,2,4-triazole ring, or benzotriazole ring.

[0150] Furthermore, the azole group in compound B is preferably a group represented by the following formula (B-1) or formula (B-2). [ka] In formula (B-1), R B1 represents a bonding site with other structures, a hydrogen atom, or a monovalent organic group, Z B1 ~Z B4 Each is independent, =CR B7 -or represents a nitrogen atom, R B7 R represents a bonding site with other structures, a hydrogen atom, or a monovalent organic group, and is included in formula (B-1). B1 and R B7 At least one of these represents a bonding site with another structure; In formula (B-2), R B2 ~R B6 Each of these independently represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, Z B5 and Z B6 Each is independent, =CR B8 -or represents a nitrogen atom, R B8 R represents a bonding site with other structures, a hydrogen atom, or a monovalent organic group, and is included in formula (B-2). B2 ~R B6 and R B8 At least one of these represents a bonding site with another structure.

[0151] In formula (B-1), R B1 represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, and is more preferably a bonding site with another structure. The above R B1 The monovalent organic group in is not particularly limited, and any known organic group can be used as long as the effects of the present invention are obtained, but it is preferably a hydrocarbon group or an amino group, and more preferably an alkyl group or an amino group. The number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, but it is preferably 1 to 10, and more preferably 1 to 4. The above amino group may be a substituted amino group or an unsubstituted amino group.

[0152] In formula (B-1), Z B1 ~Z B4Each is independent, =CR B7 - Or represents a nitrogen atom. Among them, Z B1 ~Z B4 Two of them are nitrogen atoms, and two of them are =CR B7 -The manner in which Z B1 ~Z B4 One of them is a nitrogen atom, and the other three are =CR B7 -A mode in which Z B1 ~Z B4 Three of them are nitrogen atoms, and one is =CR B7 -A configuration in which this is preferred. Also, among these, Z B1 and Z B3 This is a nitrogen atom, Z B2 and Z B4 ga = CR B7 -The manner in which Z B1 and Z B2 This is a nitrogen atom, Z B3 and Z B4 ga = CR B7 -The manner in which Z B2 This is a nitrogen atom, Z B1 , Z B3 and Z B4 ga = CR B7 -A mode in which Z B1 , Z B2 and Z B3 This is a nitrogen atom, Z B4 ga = CR B7 -A preferred configuration is Z B1 and Z B3 This is a nitrogen atom, Z B2 and Z B4 ga = CR B7 -A more preferable configuration is The above R B7 It is preferable that it is a hydrogen atom or a monovalent organic group. Also, Z B1 , Z B2 and Z B3 This is a nitrogen atom, Z B4 ga = CR B7 -If R B7 Preferably, this is a bonding site with other structures. R B7A preferred embodiment of the monovalent organic group in the above R B1 This is similar to the preferred embodiment of the monovalent organic group in [the relevant context].

[0153] R included in equation (B-1) B1 and R B7 Of these, at least one represents a binding site with another structure, and at least R B1 It is preferable that R represents a bonding site with other structures. Also, in formula (B-1), B1 Only R represents the bonding site with other structures. B7 In which each of these independently represents a hydrogen atom or a monovalent organic group, this is also one of the preferred embodiments of the present invention.

[0154] In formula (B-2), Z B5 and Z B6 Each is independent, =CR B8 - Or represents a nitrogen atom. Among them, Z B5 and Z B6 In all these cases, the embodiments represent a nitrogen atom, or Z B5 Z B6 ga = CR B8 A configuration in which each of these is represented is preferred. In equation (B-2), Z B5 and Z B6 If both represent nitrogen atoms, then R B6 It is preferable that represents the bonding site with other structures. Also, in formula (B-2), Z B5 and Z B6 Both of these represent nitrogen atoms, and R B6 In which only represents the bonding site with other structures, this is also one of the preferred embodiments of the present invention. In equation (B-2), Z B5 Z B6 ga = CR B8 When representing each of the - symbols, R B8 It is preferable that represents the bonding site with other structures. Also, in formula (B-2), Z B5 Z B6 ga = CR B8 - represents each of them, and R B8In which only represents the bonding site with other structures, this is also one of the preferred embodiments of the present invention.

[0155] In formula (B-2), R B2 ~R B5 Each of these preferably independently represents a hydrogen atom or a monovalent organic group. B2 ~R B5 A preferred embodiment of the monovalent organic group in the above R B1 This is similar to the preferred embodiment of the monovalent organic group in [the relevant context]. In formula (B-2), Z B5 Z B6 ga = CR B8 When representing each of the - symbols, R B6 R preferably represents a hydrogen atom or a monovalent organic group. B6 A preferred embodiment of the monovalent organic group in the above R B1 This is similar to the preferred embodiment of the monovalent organic group in [the relevant context]. In other cases, R B6 Preferably, Z represents a bonding site with other structures. B5 Z B6 ga = CR B8 When representing each of the - symbols, R B8 Preferably, this represents a bonding site with other structures. In formula (B-2), R B8 Preferably, represents a bonding site with other structures. Z B5 and Z B6 All of them are =CR B8 - When representing one R B8 Preferably, one represents a bonding site with another structure, and the other represents a hydrogen atom or a monovalent organic group. B8 A preferred embodiment of the monovalent organic group in the above R B1 This is similar to the preferred embodiment of the monovalent organic group in [the relevant context].

[0156] R included in equation (B-2) B2 ~R B6 and R B8 Of these, at least one represents a binding site with another structure, and at least R B6 or RB8 It is preferable that R represents a bonding site with other structures. Also, in formula (B-2), B6 and R B8 Only one of them represents a bonding site with another structure, R B6 and R B8 Of the other and R B2 ~R B5 In which each of these independently represents a hydrogen atom or a monovalent organic group, this is also one of the preferred embodiments of the present invention.

[0157] Among these, the azole group is preferably a group represented by any of the following formulas (B-3) to (B-6). [ka]

[0158] In formulas (B-3) to (B-6), R B9 ~R B20 Each of these independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. In formulas (B-3) to (B-6), R B9 ~R B20 The group is preferably a hydrocarbon group, an amino group, or a nitro group. In formulas (B-3) to (B-6), R B9 ~R B20 A preferred embodiment of the hydrocarbon group in is the R described above. B1 This is similar to the preferred embodiment of the hydrocarbon group in the above. Also, R B9 ~R B20 The amino group in this expression may be a substituted amino group or an unsubstituted amino group.

[0159] [Other silane coupling agents] Furthermore, compound B may be a compound (another silane coupling agent) that does not have a photodimerizable group or an azole group, but has an alkoxysilyl group. Other examples of silane coupling agents include, for example, the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062-0073 of Japanese Patent Publication No. 2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060-0061 of Japanese Patent Publication No. 2014-191252, the compounds described in paragraphs 0045-0052 of Japanese Patent Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067-0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0160] [ka]

[0161] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0162] Compound B may be a compound with a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular weight compound B") or a resin (hereinafter also referred to as "resin B"). Furthermore, from the viewpoint of adhesion of the cured product to the metal, it is also preferable that the photosensitive resin composition contains both low molecular weight compound B and resin B. From the viewpoint of adhesion, compound B is preferably a resin.

[0163] [Low molecular compound B] The molecular weight of low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0164] The number of photodimerizable groups in low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of alkoxysilyl groups in low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0165] The low molecular weight compound B is preferably a compound represented by formula (B1-1) or formula (B1-2) described above. Alternatively, the low molecular weight compound B may be one of the other silane coupling agents described above.

[0166] [Resin B] The weight-average molecular weight of resin B is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000.

[0167] The molar amount of photodimerizable groups in 1 g of resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0168] The molar amount of polymerizable groups in 1 g of resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0169] The molar amount of alkoxysilyl groups in 1 g of resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0170] Resin B is preferably a resin having repeating units containing a photodimerizable group and repeating units containing a radical polymerizable group, and repeating units containing an alkoxysilyl group, and more preferably a resin having repeating units containing a photodimerizable group and repeating units containing an alkoxysilyl group. Resin B may contain each of these repeating units individually or may contain two or more of them.

[0171] -Repeating units containing groups capable of photodimerization- Resin B preferably contains repeating units represented by the following formula (BL-1) as repeating units containing groups capable of photodimerization. [ka] In formula (BL-1), L L1 represents a single bond or a divalent linking group, X L1 The symbol represents a group capable of photodimerization, and R represents a hydrogen atom or a methyl group. In formula (BL-1), L L1 represents a single bond or a divalent linking group, with a divalent linking group being preferred. The above-mentioned divalent linking groups include a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10. Among these, L L1 The group is preferably represented by the following formula (BL-1-1). [ka] In formula (BL-1-1), L L4 represents a divalent linking group, LL5 represents a single bond or a divalent linking group, * represents the bonding site with the carbonyl group in formula (BL-1), and A L1 and A L2 is -O- or -NR N - represents X in (BL-1), and # represents X in (BL-1). L1 This represents the connection point. R N This is as stated above.

[0172] In formula (BL-1-1), L L4 These are hydrocarbon groups, or hydrocarbon groups with -O-, -S-, -C(=O)-, -S(=O)2- and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10.

[0173] In formula (BL-1-1), L L5 It is preferable that it is a single bond. L5 A preferred embodiment when is a divalent linking group is the above-mentioned L L4 This is similar to the preferred embodiment.

[0174] In equation (BL-1-1), A L1 and A L2 is -O- or -NR N It represents -, and preferably -O-. The above R N This is as stated above.

[0175] In formula (BL-1), X L1 A preferred embodiment is the same as the preferred embodiment of the photodimerizable group in compound B described above.

[0176] -Repeating units containing radical polymerizable groups- Resin B preferably contains repeating units represented by the following formula (BP-1) as repeating units containing radical polymerizable groups. [ka] In formula (BP-1), A P is -O- or -NR N - represents L P represents an n+1 valent linking group, X P represents a radical polymerizable group, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

[0177] In formula (BP-1), A P is -O- or -NR N - represents -O-, which is preferred. N This is as stated above.

[0178] In formula (BP-1), L P represents an n+1 valent linking group, which is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10.

[0179] In formula (BP-1), X P The preferred embodiment is the same as the preferred embodiment of the radical polymerizable group in compound B described above.

[0180] In formula (BP-1), n ​​represents an integer greater than or equal to 1, preferably an integer between 1 and 10, more preferably an integer between 1 and 5, even more preferably an integer between 1 and 3, particularly preferably 1 or 2, and most preferably 1.

[0181] - Repeating unit containing an alkoxysilyl group - Resin B preferably contains repeating units represented by the following formula (BA-2) as repeating units containing alkoxysilyl groups. [ka] In equation (BA-2), A 3 is -O- or -NR N - represents L P1 represents a divalent linking group, X P1 represents an alkoxysilyl group, and R represents a hydrogen atom or a methyl group.

[0182] In equation (BA-2), A 3 is -O- or -NR N - represents -O-, which is preferred. N This is as stated above.

[0183] In formula (BA-2), L P1 The symbol represents a divalent linking group, which is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10.

[0184] In equation (BA-2), X P1 The preferred embodiment is the same as the preferred embodiment of the alkoxysilyl group in compound B described above.

[0185] - Repeating unit containing an azole group - Resin B may also preferably contain repeating units represented by the following formula (BA-1) as repeating units containing azole groups. [ka] In formula (BA-1), L 3 represents a single bond or a divalent linking group, X 3 represents an azole group, and R represents a hydrogen atom or a methyl group. In formula (BA-1), L 3 represents a single bond or a divalent linking group. The above-mentioned divalent linking groups include a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10. Among these, L 3 A single bond, a group represented by the following formula (BA-1-1), or a group represented by the following formula (BA-1-2) is preferred. [ka] In formula (BA-1-1) or formula (BA-1-2), L 4 represents a divalent linking group, L 5 represents a single bond or a divalent linking group, L 6 represents a divalent linking group, L 7 represents a single bond or a divalent linking group, * represents the bonding site with the carbonyl group in formula (BA-1), and A 1 and A 2 is -O- or -NR N - represents X in (BA-1), and # represents X in (BA-1). 3 This represents the connection point.

[0186] In formula (BA-1-1), L 4 These are hydrocarbon groups, or hydrocarbon groups with -O-, -S-, -C(=O)-, -S(=O)2- and -NR NA group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. The above R N This is as stated above. As the hydrocarbon group mentioned above, a saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, and more preferably 2 to 10.

[0187] In formula (BA-1-1), L 5 It is preferable that it is a single bond. 5 If L is a divalent linking group, 5 These are hydrocarbon groups, or hydrocarbon groups with -O-, -S-, -C(=O)-, -S(=O)2- and -NR N A group represented by bonding with at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred.

[0188] In formula (BA-1-2), L 6 L is in equation (BA-1-1) 4 This is synonymous with the same as the preferred configuration.

[0189] In formula (BA-1-2), L 7 It is preferable that the linking group is divalent. 7 If L is a divalent linking group, 7 A preferred embodiment is L in the above formula (BA-1-1). 5 This is similar to the preferred embodiment when is a divalent linking group.

[0190] In formula (BA-1-1) or formula (BA-1-2), A 1 and A 2 is -O- or -NR N - represents -O-, which is preferred. N This is as stated above.

[0191] In equation (BA-1), X 3The preferred embodiment of the azole group in is as described above. The bonding site with other structures in the above-mentioned azole group is L in formula (BA-1). 3 This corresponds to the junction site.

[0192] Resin B may contain only one type of repeating unit represented by formula (BA-1), or it may contain two or more types. When resin B contains repeating units containing azole groups, the molar amount of azole groups in 1 g of resin B is preferably 0.001 to 5 mmol / g, and more preferably 0.01 to 1 mmol / g.

[0193] -Other repeating units- Furthermore, resin B may have other repeating units different from the repeating units represented by formula (BL-1), formula (BP-1), formula (BA-2), or formula (BA-1) described above.

[0194] [Specific examples] Specific examples of compound B include, but are not limited to, the compounds used in the examples.

[0195] [Content] The content of compound B is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one compound B, or it may contain two or more compounds B. When two or more compounds B are included, it is preferable that the total amount is within the above range.

[0196] <Compound C having an azole group and at least one group selected from the group consisting of radical polymerizable groups and photodimerizable groups> The photosensitive resin composition of the present invention preferably further comprises an azole group and a compound C having at least one group selected from the group consisting of radical polymerizable groups and photodimerizable groups. Compound C is a compound that does not contain an alkoxysilyl group. The specified resin or compound B described above shall not be considered to be compound C.

[0197] The azole group, radical polymerizable group, and photodimerizable group in compound C are the same as those in compound B, and the preferred embodiment is also the same.

[0198] Compound C may be a compound with a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular weight compound C") or a resin (hereinafter also referred to as "resin C"). Furthermore, from the viewpoint of adhesion of the cured product to the metal, it is preferable that the photosensitive resin composition contains both low molecular weight compound C and resin C. From the viewpoint of adhesion, compound C is preferably a resin.

[0199] [Low molecular compound C] The molecular weight of low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0200] The number of azole groups in low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of photodimerizable groups in low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of radical polymerizable groups in low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0201] [Resin C] The weight-average molecular weight of resin C is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000.

[0202] The molar amount of azole groups in 1 g of resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0203] The molar amount of photodimerizable groups in 1 g of resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0204] The molar amount of radical polymerizable groups in 1 g of resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0205] Resin C is preferably a resin having at least one repeating unit selected from the group consisting of repeating units having an azole group, repeating units containing a photodimerizable group, and repeating units containing a radical polymerizable group, and more preferably a resin having repeating units having an azole group and repeating units containing a photodimerizable group. Resin C may contain each of these repeating units individually or may contain two or more of them. Preferred embodiments of these repeating units are the same as preferred embodiments of these repeating units in resin B. Furthermore, resin C may have other repeating units.

[0206] [Specific examples] Specific examples of compound C include, but are not limited to, the compounds used in the examples.

[0207] [Content] The content of compound C is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one compound C, or it may contain two or more compounds C. When two or more compounds C are included, it is preferable that the total amount is within the above range.

[0208] <Compound D having an azole group but lacking an alkoxysilyl group, a radical polymerizable group, and a group capable of photodimerization> From the viewpoint of adhesion of the resulting cured product to metal, the photosensitive resin composition of the present invention preferably contains compound D, which has an azole group and does not have an alkoxysilyl group, a radical polymerizable group, or a group capable of photodimerization.

[0209] Compound D is preferably a compound represented by the following formula (D1-1) or formula (D1-2). [ka] In formula (D1-1), Z 1 ~Z 4 Each is independent, =CR 7 -or represents a nitrogen atom, R 1 R represents a hydrogen atom or a monovalent organic group. 7 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-1) does not contain alkoxysilyl groups, radical polymerizable groups, or photodimerizable groups; In formula (D1-2), Z 5 ~Z 6 Each is independent, =CR 8 -or represents a nitrogen atom, R 2 ~R 6 Each of these independently represents a hydrogen atom or a monovalent organic group, and R 8 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-2) does not contain alkoxysilyl groups, radical polymerizable groups, or photodimerizable groups.

[0210] In formula (D1-1), Z 1 ~Z 4 Each is independent, =CR 7 - Or represents a nitrogen atom. Among them, Z 1 ~Z 4 One of them is a nitrogen atom, and the other three are =CR 7 -The manner in which Z 1 ~Z 4 Two of them are nitrogen atoms, and two of them are =CR 7 -A mode in which Z 1 ~Z 4 Three of them are nitrogen atoms, and one is =CR 7 -A configuration in which this is preferred. Also, among these, Z 1 and Z 3 This is a nitrogen atom, Z 2 and Z 4 ga = CR 7 -The manner in which Z 1 and Z 2 This is a nitrogen atom, Z 3 and Z 4 ga = CR 7 -A mode in which Z 1 , Z 2 and Z 3 This is a nitrogen atom, Z 4 ga = CR 7 -A preferred configuration is Z 1 and Z 3 This is a nitrogen atom, Z 2 and Z 4 ga = CR B7 -A mode in which Z 1 , Z 2 and Z 3 This is a nitrogen atom, Z 4 ga = CR 7 -A more preferable configuration is

[0211] In formula (D1-1), R 1 It is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The number of carbon atoms in the hydrocarbon group or alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

[0212] In formula (D1-1), R 7 A preferred embodiment is R 1 It is similar to that.

[0213] In formula (D1-2), Z 5 and Z 6 Each is independent, =CR 8 - Or represents a nitrogen atom. Among them, Z 5 and Z 6 In all these cases, the embodiments represent a nitrogen atom, or Z 5 Z 6 ga = CR 8 A configuration in which each of these is represented is preferred.

[0214] In formula (D1-2), R 2 ~R 6 , R 8 Each of these is preferably independently a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0215] [Specific examples] Specific examples of compound D include, but are not limited to, the compounds used in the examples.

[0216] [Content] The content of compound D is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one compound D, or it may contain two or more compounds D. When two or more compounds D are included, it is preferable that the total amount is within the above range.

[0217] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0218] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0219] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0220] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0221] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0222] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0223] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0224] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0225] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0226] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0227] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0228] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

[0229] The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total number is within the above range.

[0230] [Photopolymerization initiator] The composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

[0231] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -1 ·cm -1 It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0232] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0233] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0234] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0235] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0236] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0237] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose maximum absorption wavelength is matched to a light source of wavelength such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

[0238] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

[0239] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0240] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0241] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0242] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0243] [ka]

[0244] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0245] As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the details of which are incorporated herein by reference.

[0246] As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505, which are incorporated herein by reference.

[0247] Furthermore, oxime compounds containing a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 2013-164471, the details of which are incorporated herein by reference.

[0248] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein by reference. Another example of an oxime compound having a nitro group is ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0249] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0250] As a photo-radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photo-polymerization initiators include the compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0251] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1 An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0252] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. RX3 ~R X14 Each of these independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0253] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0254] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0255] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0256] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0257] Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0258] Furthermore, photoradical polymerization initiators can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal. In addition, compounds represented by the following formula (I) can also be used.

[0259] [ka]

[0260] 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 or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. I01 is a group represented by formula (II), or R I00 It is the same group as R I02 ~R I04 Each of these is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0261] [ka]

[0262] In the formula, R I05 ~R I07 This is R in equation (I) above. I02 ~R I04 It is the same as this.

[0263] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0264] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0265] If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0266] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenones, Michlar's ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyranes, and indigos. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0267] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0268] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0269] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0270] If the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0271] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator refers to a compound that generates at least one of a Brønsted acid and a Lewis acid upon irradiation with light in the 200 nm to 900 nm range. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photoacid generator is preferably capable of generating acid upon photosensitization. Preferred examples of acids that are generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diphosphate esters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0272] Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oximesulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoint of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the mechanical properties of the formed film, oxime esters are preferred.

[0273] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxypolyamino compound. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds are substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By including such quinone diazide compounds, it is possible to obtain resin compositions that are sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays.

[0274] Specifically, hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisO CP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of such materials include, but are not limited to, Asahi Organic Chemicals Industry Co., Ltd.'s products: 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc.

[0275] Examples of amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0276] Furthermore, specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0277] Among these, it is preferable that the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.

[0278] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of resin. This range of quinone diazide compound content is preferable because it allows for higher sensitivity by obtaining a contrast between the exposed and unexposed areas. Furthermore, sensitizers and other additives may be added as needed.

[0279] The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but it is preferably an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later.

[0280] [ka]

[0281] In equation (OS-1), X 3 X represents an alkyl group, an alkoxy group, or a halogen atom. 3 If there are multiple instances, they may be the same or different. (See above X) 3 The alkyl and alkoxy groups in may have substituents.3 The alkyl group in is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 In X, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. 3 In this mixture, chlorine atoms or fluorine atoms are preferred as halogen atoms. In formula (OS-1), m3 represents an integer between 0 and 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 They may be the same or different. In equation (OS-1), R 34 represents an alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl halide group having 6 to 20 carbon atoms.

[0282] In equation (OS-1), m3 is 3, and X 3 The group is a methyl group, X 3 The substitution position is the ortho position, R 34 Compounds in which the group is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group are particularly preferred.

[0283] Specific examples of oximesulfonate compounds represented by formula (OS-1) include the following compounds described in paragraphs 0064-0068 of Japanese Patent Publication No. 2011-209692 and paragraphs 0158-0167 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0284] [ka]

[0285] In formula (OS-103) ~ formula (OS-105), R s1 R represents an alkyl group, aryl group, or heteroaryl group, and there may be multiple R groups. s2 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and there may be multiple Rs. s6 Each of these independently represents a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group, or alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the above may have substituents known within the range in which the effects of the present invention can be obtained.

[0286] In formula (OS-103) ~ formula (OS-105), R s2 R is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. There may be two or more R in the compound. s2 It is preferable that one or two of these are alkyl groups, aryl groups, or halogen atoms, more preferably that one is an alkyl group, aryl group, or halogen atom, and particularly preferably that one is an alkyl group and the rest are hydrogen atoms. s2 The alkyl or aryl group represented by may have substituents known within the range that the effects of the present invention can be obtained. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0287] In formulas (OS-103) to (OS-105), ns represents either 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the above may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0288] Furthermore, the compound represented by formula (OS-103) is particularly preferably a compound represented by formula (OS-106), formula (OS-110), or formula (OS-111), the compound represented by formula (OS-104) is particularly preferably a compound represented by formula (OS-107), and the compound represented by formula (OS-105) is particularly preferably a compound represented by formula (OS-108) or formula (OS-109). [ka]

[0289] In formula (OS-106) ~ formula (OS-111), R t1 R represents an alkyl group, an aryl group, or a heteroaryl group. t7 R represents a hydrogen atom or a bromine atom. t8 R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. t9 R represents a hydrogen atom, halogen atom, methyl group, or methoxy group. t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 This represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0290] In formula (OS-106) ~ formula (OS-111), R t8 This represents a hydrogen atom, a C1-C8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, preferably a C1-C8 alkyl group, more preferably a C1-C8 alkyl group, even more preferably a C1-C6 alkyl group, and particularly preferably a methyl group.

[0291] In formula (OS-106) ~ formula (OS-111), R t9 This represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom. R t2 This represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E,Z) of the oxime may be either one or a mixture. Specific examples of oximesulfonate compounds represented by formulas (OS-103) to (OS-105) above include the compounds described in paragraphs 0088 to 0095 of Japanese Patent Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0292] Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

[0293] [ka]

[0294] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or heteroaryl group. u9 A more preferable embodiment is that R is a cyano group or an aryl group. u9 A more preferable embodiment is one in which the group is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a This represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 Each of these independently represents an alkyl group or an aryl group.

[0295] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of these may bond to each other to form a ring. In this case, the ring may fused to form a fused ring with the benzene ring. u1 ~R u4 Preferably, R is a hydrogen atom, a halogen atom, or an alkyl group. u1 ~R u4 A configuration in which at least two of them bond to each other to form an aryl group is also preferred. u1 ~R u4 A configuration in which all of them are hydrogen atoms is preferred. Each of the above substituents may have further substituents.

[0296] The compound represented by the above formula (OS-101) is more preferably the compound represented by the formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture of both. Specific examples of compounds represented by formula (OS-101) include those described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Chemical Co., Ltd.).

[0297] Furthermore, compounds represented by the following structural formula are also preferred examples. [ka]

[0298] Examples of organic halogenated compounds include those described in Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-32070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, and MPHutt, "Jurnal of Heterocyclic Chemistry" 1 (No. 3), (1970), and the contents of these publications are incorporated herein by reference. In particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds are preferred examples. More preferably, s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-tri Azine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) Phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0299] Examples of organoborate compounds include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Publication No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98. Proceeding April Organic borates as described in "19-22, 1998, Chicago," etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes as described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, organoboron iodonium as described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 Examples include organoboron phosphonium complexes described in Japanese Patent Publication No. 9-188710, organoboron transition metal coordination complexes described in Japanese Patent Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, and the contents of these are incorporated herein by reference.

[0300] Examples of disulfone compounds include those described in Japanese Patent Publication No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0301] Examples of the above onium salt compounds include diazonium salts described in SISchlesinger, Photogr.Sci.Eng., 18,387 (1974) and TSBal et al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055 and Japanese Patent Publication No. 4-365049, phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056, and iodonium salts described in European Patent Nos. 104 and 143, U.S. Patent Nos. 339,049 and 410,201, Japanese Patent Publication No. 2-150848 and Japanese Patent Publication No. 2-296514. Sulfonium salts as described in the specifications of European Patents No. 370,693, 390,214, 233,567, 297,443, and 297,442; U.S. Patents No. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827; German Patents No. 2,904,626, 3,604,580, and 3,604,581; JVCrivello Examples include selenonium salts described in et al, Macromolecules, 10(6), 1307 (1977) and JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), as well as onium salts such as arsonium salts and pyridinium salts described in CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and these contents are incorporated herein by reference.

[0302] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [ka] In equation (RI-I), Ar 11Z represents an aryl group having 20 or fewer carbon atoms, which may have 1 to 6 substituents. Preferred substituents include C1-C12 alkyl groups, C2-C12 alkenyl groups, C2-C12 alkynyl groups, C6-C12 aryl groups, C1-C12 alkoxy groups, C1-C12 aryloxy groups, halogen atoms, C1-C12 alkylamino groups, C2-C12 dialkylamino groups, alkylamide groups of the alkyl group having 1 to 12 carbon atoms or arylamide groups of the aryl group having 6 to 20 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups, and C1-C12 thioaryl groups. 11 - represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar 21 Ar 22 Each of these independently represents an aryl group having 1 to 20 carbon atoms, which may have 1 to 6 substituents. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z21 -R represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R 31 , R 32 , R 33 Each of these represents an aryl group or alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may each have 1 to 6 substituents independently. Preferably, from the viewpoint of reactivity and stability, it is an aryl group. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group independently, alkylamide groups or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 31 - ∫ represents a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion. From the standpoint of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or carboxylate ion are preferred.

[0303] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0304] The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, relative to the total solid content of the resin composition. The photoacid generator may be used alone or in combination of multiple types. In the case of a combination of multiple types, it is preferable that their total amount is within the above range. Furthermore, it is preferable to use it in combination with a sensitizer in order to impart photosensitivity to the desired light source.

[0305] <Heat acid generator> The composition of the present invention may also contain a thermal acid generator. The thermal acid generator generates acid upon heating and has the effect of promoting the crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0306] The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. Furthermore, it is preferable to select a thermal acid generator that does not generate acid during drying (pre-baking: approximately 70 to 140°C) after coating the composition onto the substrate, but generates acid during the final heating (curing: approximately 100 to 400°C) after patterning by exposure and development, as this suppresses the decrease in sensitivity during development. The thermal decomposition initiation temperature is determined as the peak temperature of the lowest exothermic peak when the thermal acid generator is heated to 500°C at a rate of 5°C / min in a pressure-resistant capsule. Instruments used to measure the thermal decomposition initiation temperature include the Q2000 (manufactured by TA Instruments Corporation).

[0307] The acid generated from the thermal acid generator is preferably a strong acid, such as aryl sulfonic acids like p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids like methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or haloalkyl sulfonic acids like trifluoromethanesulfonic acid. An example of such a thermal acid generator is the one described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

[0308] In particular, from the viewpoint of having less residue in the organic film and being less likely to degrade the physical properties of the organic film, those that generate alkyl sulfonic acids with 1 to 4 carbon atoms or haloalkyl sulfonic acids with 1 to 4 carbon atoms are more preferred, such as methanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonic acid benzyl (4-hydroxyphenyl)methylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, and trifluoromethanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium Honium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4-hydroxyphenyl)methylsulfonium, trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as thermoacid generators.

[0309] Furthermore, the compound described in paragraph 0059 of Japanese Patent Publication No. 2013-167742 is also preferred as a thermal acid generator.

[0310] The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the specific resin. Including 0.01 parts by mass or more promotes the crosslinking reaction, thereby further improving the mechanical properties and solvent resistance of the organic film. Furthermore, from the viewpoint of the electrical insulation properties of the organic film, it 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.

[0311] <Base Generator> The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of nonionic base-generating compounds include those represented by formulas (B1), (B2), or (B3). [ka]

[0312] In equations (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Each of these is independently an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 They cannot become hydrogen atoms at the same time. Also, Rb 1 , Rb 2 and Rb 3 None of these have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply when the bonded carbon atom forms a carbonyl group, i.e., when it forms an amide group together with the nitrogen atom.

[0313] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0314] More specifically, Rb 1 and Rb 2The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that provides the effects of the present invention. Rb 1 and Rb 2 These may be bonded to each other to form a ring. A preferred ring is a 4-7 member nitrogen-containing heterocycle. Rb 1 and Rb 2 In particular, it is preferable that the alkyl group is a linear, branched, or cyclic alkyl group which may have substituents (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have substituents (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have substituents.

[0315] Rb 3Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb 3 It may further have substituents to the extent that it exhibits the effects of the present invention.

[0316] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2). [ka]

[0317] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 These are, respectively, Rb in equation (B1). 1 and Rb 2 It is the same as this. Rb 13The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents within a range that provides the effects of the present invention. In particular, Rb 13 An aryl alkyl group is preferred.

[0318] Rb 33 and Rb 34 Each of these is independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably 2 to 8, and still more preferably 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0319] Rb 35 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0320] Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a). [ka]

[0321] Rb 11 and Rb 12Rb in equation (B1-1) 11 and Rb 12 It is synonymous with [the above]. Rb 15 and Rb 16 The group is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and still more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and still more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and still more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and still more preferably with 7 to 11 carbon atoms), with a hydrogen atom or a methyl group being preferred. Rb 17 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0322] [ka]

[0323] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen and carbon atoms, and having 3 or more atoms on the linking chain pathway. N1 and R N2 Each of these independently represents a monovalent organic group.

[0324] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that links these linked objects in the shortest possible distance (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4. [ka]

[0325] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0326] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1). [ka]

[0327] In formula (N1), R N1 and R N2 Each of these independently represents a monovalent organic group, RC1 represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0328] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0329] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with an aliphatic hydrocarbon group being preferred. N1 and R N2 Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0330] R N1 and R N2Examples of aliphatic hydrocarbon groups that constitute the linear alkyl group include linear or branched alkyl groups, cyclic alkyl groups, groups relating to a combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched alkyl groups are preferably those having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like. The cyclic alkyl group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. The group comprising the combination of a linear alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups comprising the combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the perspective of raising the boiling point of the decomposition product bases described later, R N1 and R N2 A C5-C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1-C8 alkyl group is preferred.

[0331] R N1 and R N2These may be linked together to form a cyclic structure. In forming a cyclic structure, oxygen atoms, etc., may be present in the chain. Also, R N1 and R N2 The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0332] R C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

[0333] As a protecting group, a protecting group that decomposes upon the action of an acid or a base is preferred, and a protecting group that decomposes with an acid is particularly preferred.

[0334] Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0335] There are no specific requirements for the divalent linking group constituting L, but hydrocarbon groups are preferred, and aliphatic hydrocarbon groups are more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferable to have a divalent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, or a group which is a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0336] The preferred linking group L is specifically a linear or branched linear alkylene group, a cyclic alkylene group, a group relating to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched alkylene group is preferably composed of 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. The combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0337] The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group is preferably one with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0338] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0339] [ka]

[0340] 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.

[0341] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0342] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0343] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0344] If the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range.

[0345] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0346] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0347] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0348] 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.

[0349] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0350] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, among others. Examples of polyfunctional acrylates and methacrylates, as well as mixtures thereof, include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated; urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193; polyester acrylates as described in Japanese Unexamined Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490; and epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid. Compounds described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Publication No. 2008-292970 are also suitable. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond.

[0351] In addition, other preferred radical crosslinking agents besides those mentioned above include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent No. 4364216, etc., as well as cardo resins.

[0352] Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0353] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and these contents are incorporated herein.

[0354] Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylateing them, as described in Japanese Patent Publication No. 10-062986 with specific examples of formulas (1) and (2), can also be used as radical crosslinking agents.

[0355] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Publication No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein by reference.

[0356] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin Nakamura Chemical Industry Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0357] Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0358] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0359] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0360] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0361] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimetallate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A EO adduct dimetallate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0362] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0363] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0364] [Other crosslinking agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0365] 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, a nitrogen atom of the following urea structure, or on a triazine as structural examples. The alkoxymethyl group or acyloxymethyl group possessed by the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms. The total number of the alkoxymethyl group and acyloxymethyl group possessed by the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.

[0366]

Chemical formula

[0367] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represent a monovalent organic group, and may combine with each other to form a ring.

[0368] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

[0369]

Chemical formula

[0370] In the formula, X represents a single bond or a divalent organic group, each individual R 104 independently represents an alkyl group or an acyl group, and R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that detaches by the action of an acid, -C(R4 )2COOR 5 The group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid.)) is shown. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a + d is 5 or less, b + e is 4 or less, and c + f is 4 or less. A group that decomposes by the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, -C(R 4 )2COOR 5 Regarding 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 ) and the like can be exemplified. In the formula, R 36 ~R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above alkyl group may be either linear or branched. As the above cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those described above for preferred embodiments of alkyl and aryl groups. The above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0371] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0372] Groups that decompose upon the action of an acid to produce alkali-soluble groups, or groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, tertiary alkyl ester groups and acetal groups.

[0373] The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule, but are not limited to these.

[0374] [ka]

[0375] [ka]

[0376] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0377] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0378] Specific examples of urea-based crosslinking agents include, for example, glycoluryl-based crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, 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.

[0379] Specific examples of benzoguanamine crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0380] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0381] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. Examples include TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0382] Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0383] - Epoxy compounds (compounds containing epoxy groups) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0384] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0385] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000 Examples include FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0386] [ka]

[0387] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0388] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0389] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0390] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0391] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0392] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agents may be present by one type or by two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0393] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0394] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0395] Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0396] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content is within the above range.

[0397] <Polymerization inhibitors> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0398] Specific polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine monocerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and compounds described in paragraphs 0031-0046 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0399] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

[0400] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0401] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, an acid scavenger refers to a compound that can capture generated acids when present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferred, such as primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides, with primary amines, secondary amines, tertiary amines, and ammonium salts being preferred, and secondary amines, tertiary amines, and ammonium salts being more preferred. Preferred acid scavengers include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure; alkylamine derivatives having a hydroxyl group and / or an ether linkage; and aniline derivatives having a hydroxyl group and / or an ether linkage. When an onium structure is present, the acid scavenger is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than the acid generated by the acid generator.

[0402] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, and 1,8-diazabicyclo[5,4,0]undeker7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether linkage include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether linkage include N,N-bis(hydroxyethyl)aniline.

[0403] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylammonium hydroxide Examples include methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0404] These acid scavengers may be used individually or in combination of two or more types. The composition according to the present invention may or may not contain an acid scavenger. If it does contain an acid scavenger, the amount of acid scavenger is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0405] The ratio of acid generator to acid scavenger used is preferably 2.5 to 300 in molar ratio. Specifically, a molar ratio of 2.5 or higher is preferred from the viewpoint of sensitivity and resolution, and 300 or lower is preferred from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time from exposure to heat treatment. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0406] <Other additives> The resin composition of the present invention may contain various additives as needed, to the extent that the effects of the present invention are obtained, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregating agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, it is preferable that their total amount is 3% by mass or less of the solid content of the resin composition of the present invention.

[0407] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0408] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the amount of liquid used can be further improved. Specifically, when forming a film using a coating solution to which a composition containing a surfactant has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0409] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (all manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (all manufactured by 3M Corporation) Examples include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Corporation), etc. As fluorinated surfactants, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503 may also be used, and the contents of these are incorporated herein. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Publication No. 2011-89090, the details of which are incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0410] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0411] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0412] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BIC Chemie Co., Ltd.).

[0413] Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0414] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0415] Examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0416] Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0417] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0418] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

[0419] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0420] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0421] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals in response to thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0422] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0423] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0424] [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0425] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter for inorganic particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement methods are difficult, measurements can also be performed using centrifugal sedimentation, X-ray transmission, or laser diffraction / scattering methods.

[0426] [UV absorber] The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate, while examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0427] Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy(hydroxy) Examples include bis(hydroxyphenyl)triazine compounds such as c-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0428] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of u...

Claims

1. A resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, It contains a photopolymerization initiator, The resin has a group capable of photodimerization. Photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein the photodimerizable group is a group having a cinnamoyl structure.

3. The photosensitive resin composition according to claim 1 or 2, wherein the resin contains a radical polymerizable group.

4. A photosensitive resin composition according to any one of claims 1 to 3, further comprising compound B having an alkoxysilyl group.

5. The photosensitive resin composition according to claim 4, wherein the compound B having the alkoxysilyl group has at least one group selected from the group consisting of a photodimerizable group and a radical polymerizable group.

6. The photosensitive resin composition according to claim 4 or 5, wherein the compound B having the alkoxysilyl group has an azole group.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising an azole group and a compound C having at least one group selected from the group consisting of radical polymerizable groups and photodimerizable groups.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising compound D having an azole group and lacking an alkoxysilyl group, a radical polymerizable group, and a group capable of photodimerization.

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

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

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

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

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

14. The method for producing a cured product according to claim 13, further comprising a second exposure step of exposing the pattern obtained by the development step after the development step.

15. A method for producing a cured product according to any one of claims 12 to 14, comprising a heating step of heating the film at 50 to 450°C.

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

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