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

Abstract

The present invention provides a resin composition, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate. The resin composition comprises a cyclized resin or a resin as a precursor thereof. The resin comprises a nitrogen-containing heterocyclic structure having two or more nitrogen atoms as cyclizing atoms. The molar amount of the structure containing the nitrogen-containing heterocyclic structure that is separated from the resin when the resin is heated at 1 atmosphere and 350°C for 2 hours is 10% or less relative to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin.

Description

Technical Field

[0001] This invention relates to a resin composition, a cured product, a laminate, a method for manufacturing the cured product, and a semiconductor device. Background Technology

[0002] Cyclic resins such as polyimide are suitable for a wide range of applications due to their excellent heat resistance and insulation properties. These applications are not particularly limited; for example, in the case of semiconductor devices used in actual installation, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can be used as base films and cover films for flexible substrates.

[0003] For example, in the above-described uses, cyclized resins such as polyimide are used in the form of a resin composition comprising at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

[0004] For example, such resin compositions can be applied to a substrate to form a photosensitive film by coating, and then exposed, developed, heated, etc., as needed, thereby forming a cured product on the substrate.

[0005] The precursors of the aforementioned cyclized resins, such as polyimide precursors, are cyclized in the cured product by heating, thus becoming cyclized resins such as polyimide.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, it offers a high degree of design freedom in terms of the shape, size, and application location of the resin composition. In addition to the high performance of cyclized resins such as polyimide, the excellent manufacturing adaptability mentioned above makes the expansion of industrial applications of this resin composition increasingly promising.

[0007] For example, Patent Document 1 describes a photosensitive resin composition characterized by comprising an alkali-soluble resin and a photosensitizer, wherein one end of the alkali-soluble resin is an organic group having an unsaturated group, and at least one of the side chain and the other end has a nitrogen-containing cyclic compound.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: International Publication No. 2008 / 059808 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] In components comprising a cured material containing a cyclized resin such as polyimide and a metal (e.g., a metal layer) in contact with the cured material (e.g., an apparatus that uses the cured material as an insulating film), it is required that the metal and the cured material are not easily delaminated even after a long period of time.

[0013] The present invention aims to provide a resin composition that can produce a cured product that is not easily delaminated between the metal and the cured product even after a long period of time, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate.

[0014] means for solving technical problems

[0015] The following are examples of representative embodiments of the present invention.

[0016] A resin composition comprising a cyclized resin or a resin as a precursor thereof.

[0017] The aforementioned resin contains a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms.

[0018] The molar amount of the structure containing the nitrogen-containing heterocyclic structure that is separated from the resin by heating it at 1 atmosphere and 350°C for 2 hours is less than 10% of the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin.

[0019] <2> according to <1> The resin composition, wherein,

[0020] The aforementioned nitrogen-containing heterocyclic structure exists at the end of the aforementioned resin.

[0021] <3> according to <1> or <2> The resin composition, wherein,

[0022] The above-mentioned resin comprises a structure represented by formula (1-1) or formula (2-1) below.

[0023] [Chemical Formula 1]

[0024]

[0025] In equation (1-1), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * indicates a bonding site with other structures.

[0026] In equation (2-1), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure.2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0027] <4> A resin composition comprising a cyclized resin or a resin as a precursor thereof.

[0028] The above-mentioned resin comprises a structure represented by formula (1-1) or formula (2-1) below.

[0029] [Chemical Formula 2]

[0030]

[0031] In equation (1-1), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * indicates a bonding site with other structures.

[0032] In equation (2-1), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0033] <5> according to <1> to <4> The resin composition described in any one of the following statements, wherein,

[0034] The content of nitrogen-containing heterocyclic structures with two or more nitrogen atoms as cyclic atoms is 0.001 to 10% by mass relative to the total solid content of the composition.

[0035] <6> according to <1> to <5> The resin composition described in any one of the following statements, wherein,

[0036] The nitrogen-containing heterocyclic structure contained in the above resin includes an imidazole skeleton, a triazole skeleton, or a tetraazole skeleton.

[0037] <7> according to <1> to <6> The resin composition described in any one of the following statements, wherein,

[0038] The weight-average molecular weight of the above resins is 1,500 to 70,000.

[0039] <8> according to <1> to <7> The resin composition described in any one of the following is used to form an interlayer insulating film for a rewiring layer.

[0040] <9> A type of solidified material, which is produced by curing <1> to <8> It is made of the resin composition described in any one of the above.

[0041] <10> A laminate containing two or more layers <9> The cured material, wherein any of the aforementioned cured materials contain a metal layer between each other.

[0042] <11> A method for manufacturing a cured material, comprising applying on a substrate <1> to <8> The film forming process of forming a film using the resin composition described in any one of the above statements.

[0043] <12> according to <11> The method for manufacturing the cured material includes an exposure step of exposing the film to light and a development step of developing the film.

[0044] <13> according to <11> or <12> The method for manufacturing the cured material includes a heating step of heating the film at 50 to 450°C.

[0045] <14> A semiconductor device comprising <9> The solidified material or <10> The aforementioned laminated body.

[0046] Invention Effects

[0047] According to the present invention, a resin composition that can produce a cured product that is not easily delaminated between the metal and the cured product even after a long period of time is provided, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate. Detailed Implementation

[0048] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0049] In this specification, the numerical range indicated by the symbol “~” refers to the range including the lower limit and upper limit values ​​recorded before and after “~”, respectively.

[0050] In this specification, the term "process" means not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as they can achieve the intended function of the process.

[0051] In this specification, the designation of groups (atomic groups) without indicating whether they are substituted or unsubstituted includes both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0052] Unless otherwise specified, "exposure" in this manual includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Moreover, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0053] In this specification, "(meth)acrylate" means "acrylate" and "methacrylate" or either one; "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" or either one; and "(meth)acryloyl" means "acryloyl" and "methacryloyl" or either one.

[0054] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0055] In this specification, total solids content refers to the total mass of all components of the composition excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of components other than the solvent relative to the total mass of the composition.

[0056] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgelSuper HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgelSuper HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is unsuitable as the eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Moreover, unless otherwise specified, the detection in GPC measurements is performed using a UV ray (ultraviolet) detector with a wavelength of 254 nm.

[0057] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Moreover, unless otherwise specified, the direction in which the layers are stacked relative to the substrate layer is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in this specification, and in practice, the "upper" direction in this specification may also differ from the vertical direction.

[0058] Unless otherwise specified, in this specification, each component included in the composition may contain two or more compounds equivalent to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds equivalent to that component.

[0059] Unless otherwise specified, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0060] In this specification, the preferred combination of methods is a more preferred method.

[0061] (Resin Composition)

[0062] The resin composition according to the first aspect of the present invention comprises a cyclized resin or a resin as a precursor thereof, wherein the resin comprises a nitrogen-containing heterocyclic structure having two or more nitrogen atoms as cyclizing atoms, and the molar amount of the structure comprising the nitrogen-containing heterocyclic structure that is separated from the resin by heating the resin at 1 atmosphere and 350°C for 2 hours is 10% or less relative to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin.

[0063] The resin composition involved in the second aspect of the present invention comprises a cyclized resin or a resin as a precursor thereof, wherein the resin comprises a structure represented by the following formula (1-1) or formula (2-1).

[0064] [Chemical Formula 3]

[0065]

[0066] In equation (1-1), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * indicates a bonding site with other structures.

[0067] In equation (2-1), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0068] Hereinafter, when simply referred to as "resin composition", it is considered to include both the resin composition according to the first embodiment of the present invention and the resin composition according to the second embodiment.

[0069] Furthermore, the resin that belongs to the first aspect or is a resin that is a precursor thereof, or the resin that belongs to the second aspect or is a precursor thereof, is also referred to as a "specific resin".

[0070] The resin composition of the present invention is preferably used to form photosensitive films for exposure and development, and more preferably to form films for exposure and development using a developer containing an organic solvent.

[0071] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and more preferably to form interlayer insulating films for rewiring layers.

[0072] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive development and also for forming a photosensitive film for negative development.

[0073] In this invention, negative development refers to development in which the non-exposed parts are removed by development during exposure and development, while positive development refers to development in which the exposed parts are removed by development.

[0074] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0075] According to the resin composition of the present invention, a cured product is obtained that does not easily peel off between the metal and the cured product even after a long period of time.

[0076] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0077] To improve adhesion to metals, nitrogen-containing cyclic compounds such as tetrazolium and aminotetrazole have been used in cured products. However, from the perspective of the adhesion between metals and cured products after a long period of time, there is still room for improvement.

[0078] Through in-depth research, the inventors have discovered that when a cyclized resin or a resin as a precursor contains a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclizing atoms, and the molar amount of the structure containing the nitrogen-containing heterocyclic structure that is separated from the resin after heating the resin at 1 atmosphere and 350°C for 2 hours is 10% or less, or when a cyclized resin or a resin as a precursor contains a structure represented by formula (1-1) or formula (1-2), it is not easy for the metal and the cured product to peel off even after a long period of time.

[0079] The mechanism by which the above effects are obtained is not yet clear, but it is believed that the cured product obtained by having the resin contain a nitrogen-containing heterocyclic structure that will not be removed by heating, or a structure that is not easily decomposed by heat, i.e., the structure represented by formula (1-1) or formula (1-2), will also contain a nitrogen-containing heterocyclic structure in the resin.

[0080] It is speculated that, due to the excellent adhesion of the nitrogen-containing heterocyclic structure to the substrate (especially the metal substrate), the resin in the cured product also becomes firmly bonded to the substrate, resulting in excellent adhesion between the cured product and the substrate.

[0081] Furthermore, it is believed that, compared to the case where only the aforementioned nitrogen-containing cyclic compounds are used as low-molecular-weight components, the present invention, which contains nitrogen-containing heterocyclic structures in the resin, can reduce the low-molecular-weight components in the composition, and therefore the obtained cured product also has excellent chemical resistance.

[0082] Furthermore, it is speculated that, since the low molecular weight components in the composition can be reduced as described above, the surface uniformity (i.e., surface smoothness) of the cured product is also excellent.

[0083] Regarding the resin described in Patent Document 1, which has at least one of the side chain and the other end having a nitrogen-containing cyclic compound, it is believed that the molar amount of the structure containing the nitrogen-containing heterocyclic structure that is separated from the resin when the resin is heated at 1 atmosphere and 350°C for 2 hours will be significantly greater than 10%.

[0084] It is believed that when using this type of resin, after a long period of time, peeling is likely to occur between the metal and the cured material.

[0085] The components contained in the resin composition of the present invention will be described in detail below.

[0086] <Specific Resin>

[0087] The resin composition according to the first aspect of the present invention comprises a cyclized resin or a resin (specific resin) as a precursor thereof, wherein the resin comprises a nitrogen-containing heterocyclic structure having two or more nitrogen atoms as cyclizing atoms, and the molar amount of the structure comprising the nitrogen-containing heterocyclic structure that is separated from the resin by heating the resin at 1 atmosphere and 350°C for 2 hours is 10% or less relative to the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin.

[0088] [Nitrogen-containing heterocyclic structure]

[0089] The nitrogen-containing heterocyclic structure in the specific resin is a heterocycle containing two or more nitrogen atoms as cyclizing atoms.

[0090] The nitrogen-containing heterocyclic structure can be a monocyclic ring or a heterocyclic ring, preferably a monocyclic ring or a fused ring, more preferably a 5-membered ring or a 6-membered ring monocyclic ring or a fused ring of 5-membered rings, a fused ring of 6-membered rings, or a fused ring of 5-membered rings and 6-membered rings, more preferably a 5-membered ring monocyclic ring or a fused ring of 5-membered rings and 6-membered rings.

[0091] Wherein, when the nitrogen-containing heterocyclic structure is a heterocycle, at least one monocyclic ring constituting the heterocycle contains two or more nitrogen atoms as cyclizing atoms. That is, for example, the benzimidazole ring is equivalent to the nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as cyclizing atoms as described in this invention, but the 7-azaindole ring is not considered as the nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as cyclizing atoms as described in this invention.

[0092] Moreover, similar to the purine ring structure, the above-mentioned nitrogen-containing heterocyclic structure can have multiple nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as cyclic atoms within the heterocyclic structure.

[0093] The aforementioned nitrogen-containing heterocyclic structure may include heteroatoms other than nitrogen atoms as cyclic atoms, but a preferred embodiment of the present invention is also a nitrogen-containing heterocyclic structure that does not include heteroatoms other than nitrogen atoms as cyclic atoms. Examples of heteroatoms other than nitrogen atoms include oxygen atoms, sulfur atoms, etc.

[0094] The nitrogen-containing heterocyclic structure described above can be an aliphatic ring or an aromatic ring, but an aromatic ring is preferred.

[0095] From the viewpoint of adhesion after a long period of time, the nitrogen-containing heterocycle preferably comprises an imidazole skeleton, a triazole skeleton, or a tetraazole skeleton, more preferably an imidazole ring, a triazole ring, a tetraazole ring, or a fused ring of these rings with other rings, and even more preferably a benzimidazole ring, a triazole ring, a benzotriazole ring, a tetraazole ring, or a purine ring.

[0096] As for the other rings mentioned above, aromatic rings are preferred, 5-membered or 6-membered aromatic rings are more preferred, and benzene rings are even more preferred.

[0097] The aforementioned nitrogen-containing heterocyclic structure is preferably present at the end of a specific resin, and more preferably at the end of the main chain of a specific resin.

[0098] In this invention, the main chain refers to the longest bonded chain in the resin molecule.

[0099] Preferably, at least one of the ends of the main chain of a particular resin has the aforementioned nitrogen-containing heterocyclic structure.

[0100] The specific resin in the resin composition according to the first aspect of the present invention preferably contains a structure represented by the following formula (1-1) or formula (2-1).

[0101] The specific resin in the resin composition according to the second aspect of the present invention comprises a structure represented by the following formula (1-1) or formula (2-1).

[0102] In particular, when a particular resin is any one of polyimide, polyimide precursor, polyamide-imide or polyamide-imide precursor, it preferably contains a structure represented by the following formula (1-1).

[0103] Furthermore, when a particular resin is a polybenzoxazole or a polybenzoxazole precursor, it preferably contains a structure represented by the following formula (2-1).

[0104] [Chemical Formula 4]

[0105]

[0106] In equation (1-1), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * indicates a bonding site with other structures.

[0107] In equation (2-1), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0108] In equation (1-1), L 1 Preferably, it is a single bond or an n+1 valence hydrocarbon group, or the hydrocarbon group contains one or more groups selected from -O-, -C(=O)-, and -NR. N A group with at least one of the following structures: -S- and -S(=O)2-.

[0109] The above R N It represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0110] Moreover, L 1 The single-bonded configuration is also one of the preferred embodiments of the present invention.

[0111] In equation (1-1), R 1 The preferred method is the same as the preferred method for the nitrogen-containing heterocyclic structure described above.

[0112] In formula (1-1), n ​​is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0113] In formula (1-1), * denotes a bonding site with other structures. Here, the arrangement of the two * bonds to carbon atoms linked by covalent bonds to form the imide ring structure shown in formula (1-1) is also one of the preferred embodiments of the present invention. For example, a 5-membered ring structure is preferred as the aforementioned imide ring structure.

[0114] In equation (2-1), L v Preferably, it is a single bond or an n+1 valence hydrocarbon group, or the hydrocarbon group contains at least one group with a structure selected from -O-, -C(=O)-, -S- and -S(=O)2-.

[0115] Moreover, L 2 The single-bonded configuration is also one of the preferred embodiments of the present invention.

[0116] In equation (2-1), R 2 The preferred method is the same as the preferred method for the nitrogen-containing heterocyclic structure described above.

[0117] In formula (2-1), m is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0118] In formula (2-1), * denotes a bonding site with other structures. Here, the arrangement of the two * bonds to carbon atoms linked by covalent bonds to form the ring structure containing nitrogen and oxygen atoms shown in formula (2-1) is also one of the preferred embodiments of the present invention. For example, an oxazole ring structure is preferred as the aforementioned ring structure.

[0119] A particular resin preferably contains a structure represented by any one of the following formulas (1-2) to (1-3) as a structure containing the structure represented by formula (1-1).

[0120] [Chemical Formula 5]

[0121]

[0122] In equation (1-2) or equation (1-3), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * represents a bonding site with other structures.

[0123] In equation (1-2) or equation (1-3), L 1 R 1 and n are respectively related to L in equation (1-1) 1 R 1 The meanings of 'n' and 'n' are the same, and the preferred selection methods are also the same.

[0124] Furthermore, a particular resin preferably contains a structure represented by any one of the following formulas (2-2) to (2-3) as a structure containing the structure represented by formula (2-1).

[0125] [Chemical Formula 6]

[0126]

[0127] In equation (2-2) or equation (2-3), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0128] In equation (2-2) or equation (2-3), L 2 R 2 and m are respectively related to L in equation (2-1) 2 R 2 The meanings of 'm' and 'm' are the same, and the preferred selection methods are also the same.

[0129] When a particular resin contains the structure represented by the above formula (1-1), the particular resin preferably also contains the structure represented by the following formula (1-4).

[0130] [Chemical Formula 7]

[0131]

[0132] In equation (1-4), A 1 Represents oxygen atom or -NH-, R 115 R represents a tetravalent organic group. 114 L represents a hydrogen atom or a monovalent organic group. 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * represents a bonding site with other structures.

[0133] In equation (1-4), A 1R 114 and R 114 With A in equation (2) as described later 1 R 115 and R 114 The meanings are the same, and the preferred selection methods are also the same.

[0134] In equation (1-4), L 1 R 1 and n and L in equation (1-1) above 1 R 1 The meanings of 'n' and 'n' are the same, and the preferred selection methods are also the same.

[0135] Furthermore, when a particular resin contains a structure represented by formulas (1-4), the particular resin preferably contains a repeating unit represented by formula (2) described later.

[0136] When a particular resin contains a repeating unit represented by formula (2) described later, A in formula (1-4) is also preferred. 1 R 115 and R 114 With A in any repeating unit represented by equation (2) contained in a particular resin 1 R 115 and R 114 They have the same structure.

[0137] Furthermore, when a particular resin contains repeating units represented by formula (2) described later, it is preferable that the * in formula (1-4) is the same as R in formula (2). 111 The bonding sites.

[0138] Furthermore, when a particular resin contains the structure represented by the above formula (1-1), the particular resin preferably also contains the structure represented by the following formula (1-5).

[0139] [Chemical Formula 8]

[0140]

[0141] In equation (1-5), R 132 L represents a tetravalent organic group. 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * represents a bonding site with other structures.

[0142] In equation (1-5), R 132 R in equation (4) above 132 The meanings are the same, and the preferred selection methods are also the same.

[0143] In equation (1-5), L 1 R1 and n and L in equation (1-1) above 1 R 1 The meanings of 'n' and 'n' are the same, and the preferred selection methods are also the same.

[0144] Furthermore, when a particular resin contains a structure represented by formulas (1-5), the particular resin preferably contains a repeating unit represented by formula (4) described later.

[0145] When a particular resin contains a repeating unit represented by formula (4) described later, R in formula (1-5) is also preferred. 132 R in any repeating unit represented by equation (4) contained in a particular resin 132 They have the same structure.

[0146] Furthermore, when a particular resin contains repeating units represented by formula (4) described later, it is preferable that the * in formula (1-5) is the same as R in formula (4). 131 The bonding sites.

[0147] When a particular resin contains the structure represented by the above formula (2-1), the particular resin preferably also contains the structure represented by the following formula (2-4).

[0148] [Chemical Formula 9]

[0149]

[0150] In equation (2-4), R 122 R represents a tetravalent organic group. 124 L represents a hydrogen atom or a monovalent organic group. 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0151] In equation (2-4), R 122 and R 124 R in equation (3) will be discussed later. 122 and R 124 The meanings are the same, and the preferred selection methods are also the same.

[0152] In equation (2-4), L 2 R 2 and m and L in the above equation (2-1) 2 R 2 The meanings of 'm' and 'm' are the same, and the preferred selection methods are also the same.

[0153] Furthermore, when a particular resin contains a structure represented by formulas (2-4), the particular resin preferably contains a repeating unit represented by formula (3) described later.

[0154] When a particular resin contains a repeating unit represented by formula (3) described later, R in formula (2-4) is also preferred. 122 and R 124 R in any repeating unit represented by equation (3) contained in a particular resin 122 and R 124 They have the same structure.

[0155] Furthermore, when a particular resin contains a repeating unit represented by formula (3) described later, it is preferable that the * in formula (2-4) is the same as R in formula (3). 121 The bonding sites.

[0156] When a particular resin contains the structure represented by the above formula (2-1), the particular resin preferably also contains the structure represented by the following formula (2-5).

[0157] [Chemical Formula 10]

[0158]

[0159] In equation (2-5), R 134 L represents a tetravalent organic group. 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

[0160] In equation (2-5), R 134 R in the following equation (X) 134 The meanings are the same, and the preferred selection methods are also the same.

[0161] In equation (2-5), L 2 R 2 and m and L in the above equation (1-1) 2 R 2 The meanings of 'm' and 'm' are the same, and the preferred selection methods are also the same.

[0162] Furthermore, when a particular resin contains a structure represented by formulas (2-5), the particular resin preferably contains a repeating unit represented by formula (X) described later.

[0163] When a particular resin contains a repeating unit represented by formula (X) described later, R in formula (2-5) is also preferred. 134 R in any repeating unit represented by formula (X) contained in a particular resin 134 They have the same structure.

[0164] Furthermore, when a particular resin contains repeating units represented by formula (X) described later, it is preferable that the * in formula (1-5) is the same as the R in formula (X).133 The bonding sites.

[0165] The following are specific examples of structures containing nitrogen-containing heterocyclic structures (which contain two or more nitrogen atoms as cyclic atoms) in a particular resin, but the present invention is not limited thereto. In the following structures, * indicates a bonding site with other structures.

[0166] [Chemical Formula 11]

[0167]

[0168] The content (also referred to as "content A") of nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as cyclic atoms is preferably 0.001 to 10% by mass relative to the total solid content of the composition, more preferably 0.01 to 8% by mass, and even more preferably 0.1 to 5% by mass.

[0169] The aforementioned content A includes not only the content of the nitrogen-containing heterocyclic structure contained in the specific resin, but also the content of compounds having nitrogen-containing heterocyclic structures (e.g., migration inhibitors described later) in addition to the specific resin.

[0170] That is, when the composition contains only a specific resin as a compound containing the above-mentioned nitrogen-containing heterocyclic structure, the above-mentioned content A is a value expressed by the following formula.

[0171] Content A = (Mass of specific resin content × Molecular weight of the aforementioned heterocycles contained in the specific resin / Molecular weight of the specific resin) / (Total solids content) × 100

[0172] Furthermore, when the composition contains a specific resin and component 1 (e.g., the migration inhibitor described later) as a compound containing the above-mentioned nitrogen-containing heterocyclic structure, the above-mentioned content A is a value expressed by the following formula.

[0173] Content A = {(Mass content of a specific resin × Molecular weight of the aforementioned heterocycles contained in the specific resin / Molecular weight of the specific resin) + (Mass content of component 1 × Molecular weight of the aforementioned heterocycles contained in component 1 / Molecular weight of component 1)} / (Total solids content) × 100

[0174] Furthermore, the content of nitrogen-containing heterocyclic structures containing two or more nitrogen atoms as cyclic atoms is preferably 1 to 4 moles, more preferably 1 to 2 moles, relative to 1 mole of a specific resin.

[0175] [The proportion of the molar amounts of the structures containing the above-mentioned nitrogen-containing heterocyclic structures that have been removed]

[0176] Here, the proportion of the molar amount of the structure containing the nitrogen-containing heterocyclic structure that was separated from the resin when the resin was heated at 1 atmosphere and 350°C for 2 hours is calculated as follows.

[0177] One mole of resin was placed in a sealed container and heated at 350°C for 2 hours under 1 atmosphere pressure. The amount of structures including nitrogen-containing heterocyclic structures separated by HPLC (high-speed liquid chromatography) was then quantified.

[0178] Then, calculate the above percentage (%) according to the following formula.

[0179] Proportion (%) = (Molar amount of the structure containing nitrogen-containing heterocyclic structure removed) / (Molar amount of the structure containing the above-mentioned nitrogen-containing heterocyclic structure contained in the resin)

[0180] The aforementioned percentage is 10% or less, preferably 8% or less, and more preferably 5% or less. Furthermore, the lower limit of the aforementioned percentage is not particularly limited and can be 0%.

[0181] The weight-average molecular weight of the specific resin is preferably 1,500 to 70,000, more preferably 10,000 to 50,000.

[0182] The specific resin is a cyclized resin or its precursor.

[0183] Cyclic resins are preferably resins that contain an imide ring structure or an oxazole ring structure in their main chain structure.

[0184] Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide.

[0185] The precursor of a cyclized resin refers to a resin whose chemical structure changes through external stimulation to become a cyclized resin. Preferably, it is a resin whose chemical structure changes through heat to become a cyclized resin, and more preferably, it is a resin that forms a ring structure through a ring-closing reaction caused by heat to become a cyclized resin.

[0186] Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0187] That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide precursor as a specific resin.

[0188] The resin composition of the present invention preferably contains a polyimide or a polyimide precursor as a specific resin.

[0189] Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0190] When a particular resin has a free radical polymerizable group, the resin composition of the present invention preferably contains a free radical polymerization initiator (described later), more preferably contains both the free radical polymerization initiator (described later) and the free radical crosslinking agent (described later). A sensitizer (described later) can be further included as needed. For example, a negative photosensitive film can be formed from such resin compositions of the present invention.

[0191] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0192] When a particular resin has an acid-degrading group, the resin composition of the present invention preferably contains a photoacid-generating agent, as described later. For example, such resin compositions of the present invention can be used to form chemically amplified positive or negative photosensitive films.

[0193] [Polyimide precursor]

[0194] The polyimide precursor used in this invention is not particularly limited to any particular type, but preferably contains repeating units represented by the following formula (2).

[0195] [Chemical Formula 12]

[0196]

[0197] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0198] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, with oxygen atom being preferred.

[0199] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups containing aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups containing the cyclic atoms of the aforementioned cyclic aliphatic and aromatic groups can be replaced by groups containing heteroatoms. As a preferred embodiment of the present invention, R can be exemplified. 111Examples of groups represented by -Ar- and -Ar-L-Ar- are provided, with groups represented by -Ar-L-Ar- being particularly preferred. Here, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. The preferred ranges are as described above.

[0200] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0201] Specifically, the preferred diamine is a diamine comprising a straight-chain 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; more preferably, a diamine comprising an aromatic group having 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups of the cyclic atoms of the aforementioned cyclic aliphatic and aromatic groups can be replaced by groups containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0202] [Chemical Formula 13]

[0203]

[0204] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0205] In the formula, * indicates the bonding site with other structures.

[0206] As a diamine, specifically, examples include at least one diamine selected from the following: 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) ... Hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 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'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane 3,3'-Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 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, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5- Diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, [4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl The following compounds are listed: 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0207] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0208] Furthermore, the diamine having two or more alkylene glycol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may be preferred.

[0209] From the perspective of the flexibility of the obtained organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0210] Moreover, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0211] Equation (51)

[0212] [Chemical Formula 14]

[0213]

[0214] In equation (51), R 50 ~R 57 Each can be independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0215] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0216] [Chemical Formula 15]

[0217]

[0218] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0219] Examples of diamines that impart 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. One or more of these may be used.

[0220] R in equation (2) 115 This indicates a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0221] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0222] [Chemical Formula 16]

[0223]

[0224] In equation (5), R 112 It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond, a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0225] Specifically, R 115 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As equivalent to R... 115 The structure of the polyimide precursor can contain only one type of tetracarboxylic acid dianhydride residue or more than two types.

[0226] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0227] [Chemical Formula 17]

[0228]

[0229] In equation (O), R 115 R represents a tetravalent organic group. 115 The preferred range is the same as R in equation (2). 115 They have the same meaning and the same preferred range.

[0230] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic 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 thereof having 1 to 6 carbon atoms.

[0231] Furthermore, as a preferred example, one could cite tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0232] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0233] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymerizable group, more preferably both contain polymerizable groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of cross-linking through the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having olefinic unsaturated bonds is preferred.

[0234] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0235] [Chemical Formula 18]

[0236]

[0237] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0238] In equation (III), * indicates the bonding site with other structures.

[0239] In equation (III), R 201 It represents alkylene groups with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, cycloalkylene groups, or polyalkylene groups.

[0240] R 201 Preferred examples include alkylene compounds such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxides; more preferably, alkylene compounds such as vinyl and propenyl, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxides; and even more preferably, alkylene compounds such as vinyl and propenyl or polyalkylene oxides.

[0241] In this invention, polyalkylene oxide refers to a group in which two or more alkene oxides are directly bonded together. The alkylene oxides in the multiple alkene oxides contained in the polyalkylene oxide can be the same or different.

[0242] When a polyalkylene oxide contains multiple alkene oxides with different alkylene oxides, the arrangement of the alkene oxides in the polyalkylene oxide can be random, block-shaped, or alternating.

[0243] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0244] Furthermore, the aforementioned alkylene groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0245] Furthermore, the number of alkene oxides contained in the polyalkylene oxide (the number of repetitions of the polyalkylene oxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0246] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups bonded to multiple ethyleneoxy and multiple propyleneoxy groups are preferred as polyalkyleneoxy groups; polyvinyloxy or polypropyleneoxy groups are more preferred; and polyvinyloxy groups are even more preferred. Among the aforementioned groups bonded to multiple ethyleneoxy and multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred manner for the repetition of the ethyleneoxy groups, etc., is as described above.

[0247] In equation (2), in R 113 For the case of hydrogen atoms or R 114 In the case of hydrogen atoms, polyimide precursors can form conjugated salts with tertiary amine compounds having olefinically unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such tertiary amine compounds having olefinically unsaturated bonds.

[0248] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it is decomposed by the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. It is preferred to use acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0249] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0250] Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0251] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0252] 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 this invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased.

[0253] Equation (2-A)

[0254] [Chemical Formula 19]

[0255]

[0256] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0257] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 They have the same meaning and the same preferred range.

[0258] R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0259] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. Moreover, it may contain structural isomers of the repeating unit represented by formula (2). Furthermore, in addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0260] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, further 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 end units can be repeating units represented by formula (2).

[0261] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 1,500 to 100,000, more preferably 1,500 to 70,000, further preferably 5,000 to 70,000, particularly preferably 10,000 to 50,000, and most preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, further preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000.

[0262] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0263] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0264] Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0265] [Polyimide]

[0266] The polyimide used in this invention can be an alkali-soluble polyimide, or a polyimide soluble in a developer solution mainly composed of organic solvents.

[0267] In this specification, alkali-soluble polyimide refers to polyimide in which 0.1 g or more is dissolved in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve 0.5 g or more of polyimide, and more preferably 1.0 g or more of polyimide. There is no particular upper limit to the above-mentioned dissolution amount, but it is preferably 100 g or less.

[0268] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyimide is preferably a polyimide having multiple imide structures in the main chain.

[0269] In this specification, "main chain" refers to the longest bonded chain in the polymer compound that constitutes the resin, and "side chain" refers to the bonded chain other than the main chain.

[0270] -Fluorine atom-

[0271] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably provided with fluorine atoms.

[0272] Fluorine atoms are preferably contained, for example, in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) described later 131 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) described later 131 .

[0273] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0274] -Silicon atom-

[0275] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably composed of silicon atoms.

[0276] Silicon atoms are preferably contained, for example, in the repeating unit represented by equation (4) described later. 131 More preferably, R is included in the repeating unit represented by the following formula (4) as an organically modified (poly)siloxane structure. 131 .

[0277] Furthermore, the silicon atoms or the organically modified (poly)siloxane structure described above may be included in the side chain of the polyimide, but preferably in the main chain of the polyimide.

[0278] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, more preferably 20% by mass or less.

[0279] -ene unsaturated bond-

[0280] From the viewpoint of the strength of the obtained organic membrane, polyimide preferably has olefinic unsaturated bonds.

[0281] Polyimide can have olefinic unsaturated bonds at the end of the main chain or in the side chain, preferably in the side chain.

[0282] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0283] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) described later 131 More preferably, R is included as a group having an olefinic unsaturated bond in the repeating unit represented by formula (4) described later. 132 Or R in the repeating unit represented by equation (4) described later 131 .

[0284] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 131 More preferably, R is included as a group having an olefinic unsaturated bond in the repeating unit represented by formula (4) described later. 131 .

[0285] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, etc., which have vinyl groups that are directly bonded to the aromatic ring and can be substituted, (meth)acrylamido, (meth)acryloyloxy, and groups represented by the following formula (IV).

[0286] [Chemical Formula 20]

[0287]

[0288] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0289] In equation (IV), R 21 The group represents an alkylene group with 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkoxy group with 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, especially preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, especially preferably 1 to 3) or a group formed by combining two or more of these.

[0290] Furthermore, the alkylene group having 2 to 12 carbon atoms can be any of the following: linear, branched, cyclic, or a combination thereof.

[0291] As the aforementioned 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.

[0292] Among them, R 21 Preferably, it is a group represented by any one of the following formulas (R1) to (R3), and more preferably, it is a group represented by formula (R1).

[0293] [Chemical Formula 21]

[0294]

[0295] In formulas (R1) to (R3), L represents a single bond or an alkylene group with 2 to 12 carbon atoms, a (poly)alkene group with 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 other structures; and ● represents a connection with R in formula (IV). 21 The bonding sites of the bonded oxygen atoms.

[0296] In formulas (R1) to (R3), the preferred form of L is an alkylene group having 2 to 12 carbon atoms or a (poly)alkene group having 2 to 30 carbon atoms, which is the same as that of R above. 21 The preferred configurations are the same for alkylene groups with 2 to 12 carbon atoms or (poly)alkoxide groups with 2 to 30 carbon atoms.

[0297] In formula (R1), X is preferably an oxygen atom.

[0298] In equations (R1) to (R3), * has the same meaning as * in equation (IV), and the preferred method is also the same.

[0299] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having hydroxyl groups, such as phenolic hydroxyl groups, with a compound having isocyanate groups and olefinic unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0300] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having hydroxyl and olefinic unsaturated bonds (e.g., 2-hydroxyethyl methacrylate, etc.).

[0301] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having hydroxyl groups, such as phenolic hydroxyl groups, with a compound having glycidyl and olefinic unsaturated bonds (e.g., glycidyl methacrylate).

[0302] In formula (IV), * indicates a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

[0303] The amount of olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0304] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0305] Polyimides can contain polymeric groups other than those with olefinic unsaturated bonds.

[0306] Examples of polymerizable groups other than those with olefinic unsaturated bonds include cyclic ether groups such as epoxy and oxobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups.

[0307] For example, polymerizable groups other than those having olefinic unsaturated bonds are preferably included in R in the repeating unit represented by formula (4) described later. 131 .

[0308] The amount of polymerizable groups other than those having olefinic unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, relative to the total mass of the polyimide.

[0309] -Polar conversion group-

[0310] Polyimides can possess polar conversion groups such as acid-degradable groups. The acid-degradable groups in polyimides interact with the R group in formula (2) above. 113 and R 114 The acid-decomposing groups described in the text are the same, and the preferred methods are also the same.

[0311] The polarity conversion base, for example, is contained in the repeating unit represented by equation (4) described later. 131 R 132 Ends of polyimide, etc.

[0312] -Acid Value-

[0313] When polyimide is used for alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0314] Furthermore, the 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.

[0315] Furthermore, when polyimide is used in development using a developer solution with organic solvent as the main component (e.g., "solvent development" described below), 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.

[0316] The acid value mentioned above is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0317] Furthermore, from the viewpoint of balancing storage stability and developability, acid groups containing polyimide with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred.

[0318] pKa is the equilibrium constant Ka value expressed as the negative logarithm of a dissociation reaction in which an acid releases hydrogen ions. In this specification, unless otherwise specified, pKa is set to a value calculated based on ACD / ChemSketch (registered trademark). Alternatively, the value described in the "5th Revised Edition of the Basic Chemistry Handbook" compiled by the Chemical Society of Japan can be consulted.

[0319] Furthermore, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant.

[0320] As such an acid group, the polyimide preferably contains at least one selected from carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0321] -Phenolic hydroxyl-

[0322] From the viewpoint of making the development speed appropriate for alkaline developing solutions, polyimide preferably has phenolic hydroxyl groups.

[0323] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0324] Phenolic hydroxyl groups are preferably contained in the repeating unit represented by formula (4) described later, for example, R. 132 Or R in the repeating unit represented by equation (4) described later 131 .

[0325] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0326] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains repeating units represented by the following formula (4).

[0327] [Chemical Formula 22]

[0328]

[0329] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0330] When it has a polymerizable group, the polymerizable group can be located at R 131 and R 132 In at least one of them, it may also be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below.

[0331] Equation (4-1)

[0332] [Chemical Formula 23]

[0333]

[0334] In equation (4-1), R 133 It is a polymerizable group, and the other groups have the same meaning as in formula (4).

[0335] Equation (4-2)

[0336] [Chemical Formula 24]

[0337]

[0338] R 134 and R 135 At least one of them is a polymeric group, and if it is not a polymeric group, it is an organic group. The other groups have the same meaning as in formula (4).

[0339] Examples of polymerizable groups include groups containing olefinic unsaturated bonds as described above, or crosslinking groups other than those containing olefinic unsaturated bonds.

[0340] R 131 This represents a divalent organic group. Examples of divalent organic groups include R in formula (2). 111 For the same functional groups, the preferred range is also the same.

[0341] Moreover, as R 131 Examples of diamines include the diamine residue remaining after the amino group of the diamine is removed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) of a polyimide precursor can be cited. 111 Examples.

[0342] From the perspective of more effectively suppressing warping during calcination, R 131Preferably, it is a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine containing a total of two or more diamines in one molecule, either an ethylene glycol chain or a propylene glycol chain, and even more preferably, it is a diamine residue that does not contain an aromatic ring.

[0343] Examples of diamines containing two or more diamines in a single molecule, such as JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., are not limited to these.

[0344] R 132 This represents a tetravalent organic group. Examples of tetravalent organic groups include R in formula (2). 115 For the same functional groups, the preferred range is also the same.

[0345] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C (=O)- portions in the above formula (4) to form a fused ring.

[0346] Moreover, R 132 Examples include the tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of a polyimide precursor can be cited. 115 Examples. From the viewpoint of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0347] R is also preferred 131 and R 132 At least one of them has an OH group. More specifically, as R 131 Examples of preferred embodiments include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, as well as (DA-1) to (DA-18) mentioned above. 132 Examples of better examples include (DAA-1) to (DAA-5).

[0348] Furthermore, the polyimide preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0349] Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0350] Furthermore, to improve the storage stability of the resin composition, the main chain ends of the polyimide are preferably capped with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and active monoester compounds. Among these, monoamines are more preferably used. Examples of 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and various different end groups can be introduced by reacting multiple end-capping agents.

[0351] -Imidization rate (ring-closure rate)-

[0352] From the perspective of the obtained organic film's strength and insulation properties, the imidization rate (also known as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0353] There is no specific upper limit to the imidization rate mentioned above; it can be below 100%.

[0354] For example, the imidization rate described above can be measured using the following method.

[0355] The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure, i.e., 1377 cm⁻¹, was determined. -1 The peak intensity P1 near the target was determined. Next, the polyimide was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity at 1377 cm⁻¹.-1 The peak intensity P2 is nearby. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula.

[0356] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0357] Polyimide can have a composition consisting of all 1 type of R 131 or R 132 The repeating unit represented by the above equation (4) can also have R consisting of two or more different kinds. 131 or R 132 The repeating unit represented by the above formula (4). Moreover, in addition to the repeating unit represented by the above formula (4), polyimide may also contain other types of repeating units. For example, the repeating unit represented by the above formula (2) can be cited as another type of repeating unit.

[0358] For example, polyimides can be synthesized by: reacting a tetracarboxylic dianhydride with a diamine (with a portion replaced by a monoamine, i.e., a capping agent) at low temperature; reacting a tetracarboxylic dianhydride (with a portion replaced by an anhydride, a monoacyl chloride compound, or an active monoester compound, i.e., a capping agent) with a diamine at low temperature; obtaining a diester from a tetracarboxylic dianhydride and an alcohol, followed by reacting the diester with a diamine (with a portion replaced by a monoamine, i.e., a capping agent) and a condensing agent; obtaining a diester from a tetracarboxylic dianhydride and an alcohol, followed by acylation of the remaining dicarboxylic acid and reacting it with a diamine (with a portion replaced by a monoamine, i.e., a capping agent); and then synthesizing a polyimide precursor by completely imidizing it using a known imidization reaction, or by stopping the imidization reaction midway and introducing a partial imide structure, or by further mixing the fully imidized polymer and its polyimide precursor to introduce a partial imide structure. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0359] The weight-average molecular weight (Mw) of the polyimide is preferably 1,500 to 100,000, more preferably 1,500 to 70,000, further preferably 5,000 to 70,000, particularly preferably 10,000 to 50,000, and most preferably 15,000 to 40,000. By setting the weight-average molecular weight to 1,500 or higher, the flexural strength of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher is particularly preferred.

[0360] Furthermore, the number average molecular weight (Mn) of the polyimide is preferably 1,000 to 40,000, more preferably 2,000 to 40,000, even more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000.

[0361] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0362] Furthermore, when the resin composition contains multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimides are used as a single resin are each within the aforementioned ranges.

[0363] [Polybenzoxazole precursor]

[0364] The structure of the polybenzoxazole precursor used in this invention is not particularly limited, but it preferably contains repeating units represented by the following formula (3).

[0365] [Chemical Formula 25]

[0366]

[0367] In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0368] In equation (3), R 123 and R 124 respectively with R in equation (2) 113 The meanings are the same, and the preferred range is also the same. That is, at least one of them is preferably a polymeric group.

[0369] In equation (3), R 121 This indicates a divalent organic group. Preferably, the divalent organic group comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 The preferred choice is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0370] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred.

[0371] As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkylene group.

[0372] Examples of dicarboxylic acids containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylhimelic acid. Diacid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid Acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[0373] [Chemical Formula 26]

[0374]

[0375] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0376] As a dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH groups is more preferred.

[0377] [Chemical Formula 27]

[0378]

[0379] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0380] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

[0381] In equation (3), R 122 This represents a tetravalent organic group. As a tetravalent organic group, it is related to R in the above formula (2). 115 They have the same meaning and the same preferred range.

[0382] Moreover, R 122 Preferably, the group is derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis... Diaminophenols include bis(4-amino-3-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)methane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These diaminophenols can be used alone or in combination.

[0383] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic groups are preferred.

[0384] [Chemical Formula 28]

[0385]

[0386] In the formula, X1 represents -o-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Furthermore, R... 122 The structure represented by the above formula is also preferred. R 122 When the structure is represented by the above formula, among the four * and #, it is preferable that any two are R in formula (3). 122 The bonding sites of the nitrogen atoms are the same as those of the other two atoms, which are related to R in equation (3). 122The bonding sites of the bonded oxygen atoms are preferably two associating with R in equation (3). 122 The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms or the two asterisks are related to R in equation (3). 122 The bonding sites of the nitrogen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the bonded oxygen atoms are further preferably two as R in equation (3). 122 The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms.

[0387] The diaminophenol derivative is preferably a compound represented by formula (As).

[0388] [Chemical Formula 29]

[0389]

[0390] In formula (As), R1 is an organic group selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl, alkoxy, acyloxy, or cyclic alkyl, and may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl, alkoxy, acyloxy, or cyclic alkyl, and may be the same or different.

[0391] [Chemical Formula 30]

[0392]

[0393] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0394] In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R3, will make the carbonyl carbon of the amide bond closer to the hydroxyl group, which is especially preferred from the perspective of further improving the effect of increasing the cyclization rate when curing at low temperature.

[0395] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, the high transparency to i-rays and the high cyclization rate during low-temperature curing are maintained, which is therefore preferred.

[0396] Furthermore, in the above formula (As), R1 is preferably an alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene involved in R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, considering the maintenance of high transparency to i-rays and high cyclization rate during low-temperature curing while maintaining sufficient solubility in solvents and obtaining a well-balanced polybenzoxazole precursor, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred.

[0397] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, which are incorporated herein by reference.

[0398] Specific examples of the structures of bisaminophenol derivatives represented by the above formula (As) can be found in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, which are incorporated herein by reference. However, this is not the only possible explanation.

[0399] In addition to the repeating unit in formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.

[0400] From the viewpoint of being able to suppress the warping that accompanies the ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0401] [Chemical Formula 31]

[0402]

[0403] In equation (SL), Z has structures a and b, and R 1s R is a hydrocarbon group consisting of 1 to 10 hydrogen atoms or carbon atoms. 2s R is a hydrocarbon group with 1 to 10 carbon atoms. 3s R 4s R 5s R 6s At least one of the radicals is an aromatic group, and the remaining part consists of hydrogen atoms or organic groups with 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, structure a is 5–95 mol%, structure b is 95–5 mol%, and a+b is 100 mol%.

[0404] In equation (SL), Z, as a preferred option, can be represented by R in structure b. 5s and R 6sThe molecular weight is phenyl. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, while simultaneously achieving the effects of suppressing warpage and improving solvent solubility.

[0405] When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R in formula (2). 115 Examples.

[0406] For example, the weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 1,500 to 70,000, more preferably 18,000 to 30,000, even more preferably 20,000 to 29,000, and particularly preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 1,000 to 14,000, more preferably 7,200 to 14,000, even more preferably 8,000 to 12,000, and particularly preferably 9,200 to 11,200.

[0407] The molecular weight dispersion of the aforementioned polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzoxazole precursor; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and still even more preferably 2.2 or less.

[0408] Furthermore, when the resin composition contains multiple polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polybenzoxazole precursors as a single resin are each within the aforementioned ranges.

[0409] [Polybenzoxazole]

[0410] As for polybenzoxazole, there is no particular limitation as long as it is a polymeric compound having a benzoxazole ring. A compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the polymerizable group, a free radical polymerizable group is preferred. Furthermore, a compound represented by the following formula (X) and having a polar conversion group such as an acid-decomposing group can also be used.

[0411] [Chemical Formula 32]

[0412]

[0413] In equation (X), R 133 R represents a divalent organic group. 134 It represents a tetravalent organic group.

[0414] When a polar conversion group such as a polymerizable group or an acid-decomposable group is present, the polymerizable group or the acid-decomposable group can be located at R. 133 and R 134 At least one of them may also be located at the end of polybenzoxazole as shown in formula (X-1) or formula (X-2) below.

[0415] Equation (X-1)

[0416] [Chemical Formula 33]

[0417]

[0418] In equation (X-1), R 135 and R 136 At least one of them is a polar conversion group such as a polymerizable group or an acid-decomposable group. If it is not a polymerizable group or an acid-decomposable group, it is an organic group. The other groups have the same meaning as in formula (X).

[0419] Equation (X-2)

[0420] [Chemical Formula 34]

[0421]

[0422] In equation (X-2), R 137 One group is a polar conversion group such as a polymerizable group or an acid-decomposable group; the others are substituents. The other groups have the same meaning as in formula (X).

[0423] The polar conversion groups, such as polymerizable groups or acid-degradable groups, have the same meaning as the polymerizable groups described in the polymerizable groups polymerized in the above-mentioned polyimide precursors.

[0424] R 133 This indicates a divalent organic group. Examples of divalent organic groups include aliphatic or aromatic groups. As a specific example, R in formula (3) of the polybenzoxazole precursor is an example. 121 Examples. Furthermore, its preferred example is related to R. 121 same.

[0425] R 134 This indicates a tetravalent organic group. Examples of tetravalent organic groups include R in formula (3) of the polybenzoxazole precursor. 122 Examples. Furthermore, its preferred example is related to R. 122 same.

[0426] For example, as R 122 The four bonds of the exemplified tetravalent organic group bond with the nitrogen and oxygen atoms in formula (X) above to form a fused ring. For example, R 134 When the organic group is one of the following, the following structure is formed. In the following structures, * indicates the bonding site with the nitrogen or oxygen atom in formula (X).

[0427] [Chemical Formula 35]

[0428]

[0429] The oxazoleization rate of polybenzoxazole is preferably 85% or higher, more preferably 90% or higher. There is no particular upper limit, and it can be 100%. With an oxazoleization rate of 85% or higher, the membrane shrinkage caused by ring closure during oxazoleization by heating is reduced, thereby effectively suppressing warping.

[0430] For example, the oxazolization rate described above can be measured by the following method.

[0431] The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm⁻¹ derived from the amide structure of the precursor was determined. -1 The peak intensity Q1 is located near the 1490 cm⁻¹. Next, using [the data]... -1 The absorption intensity of the aromatic ring observed nearby was normalized. After heat-treating the polybenzoxazole precursor at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the 1650 cm⁻¹ value was determined. -1 The peak intensity Q2 is near, and is utilized at 1490 cm⁻¹. -1 The absorption intensity of the aromatic ring observed nearby was normalized. Using the normalized values ​​of the obtained peak intensities Q1 and Q2, the oxazolization rate of polybenzoxazole can be calculated according to the following formula.

[0432] Oxazoleization rate (%) = (Normalized value of peak intensity Q1 / Normalized value of peak intensity Q2) × 100

[0433] Polybenzoxazole can have a composition consisting entirely of one R 131 or R 132 The repeating unit of the above equation (X) can also have more than two different kinds of R. 131 or R 132 The repeating unit of the above formula (X). Moreover, in addition to the repeating unit of the above formula (X), polybenzoxazole may also contain other types of repeating units.

[0434] For example, making a diaminophenol derivative with R 133Polybenzoxazole precursors are obtained by reacting dicarboxylic acids or compounds selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazoleized by a known oxazoleization reaction method to obtain polybenzoxazole.

[0435] In addition, in the case of dicarboxylic acids, in order to improve reaction yield, an active ester-type dicarboxylic acid derivative, such as 1-hydroxy-1,2,3-benzotriazole, can be used in advance.

[0436] The weight-average molecular weight (Mw) of polybenzoxazole is preferably 1,500 to 70,000, more preferably 5,000 to 70,000, even more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight-average molecular weight to 1,500 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more polybenzoxazoles are contained, it is preferable that at least one polybenzoxazole has a weight-average molecular weight within the above range.

[0437] Furthermore, the number average molecular weight (Mn) of polybenzoxazole is preferably 1,000 to 14,000, more preferably 7,200 to 14,000, even more preferably 8,000 to 12,000, and particularly preferably 9,200 to 11,200.

[0438] The molecular weight dispersion of the aforementioned polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular limitation on the upper limit of the molecular weight dispersion of polybenzoxazole; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and still even more preferably 2.2 or less.

[0439] Furthermore, when the resin composition contains multiple polybenzoxazoles as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polybenzoxazoles are used as a single resin are each within the aforementioned ranges.

[0440] [Polyamide-imide precursor]

[0441] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2).

[0442] [Chemical Formula 36]

[0443]

[0444] In formula (PAI-2), R117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 It represents a hydrogen atom or a monovalent organic group.

[0445] In formula (PAI-2), R 117 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0446] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0447] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0448] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms being preferably replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0449] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0450] Moreover, R 117 Preferably, the compound is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method.

[0451] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0452] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

[0453] Examples of halogenable tricarboxylic acid compounds used to manufacture polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0454] These tricarboxylic acid compounds can be used in one or more forms.

[0455] Specifically, as a tricarboxylic acid compound, it is preferable to be a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound comprising 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 through single bonds or linking groups.

[0456] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds formed by the linkage of phthalic acid (or phthalic anhydride) with benzoic acid through single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene oxide.

[0457] These compounds can be compounds formed by anhydride conversion of two carboxyl groups (e.g., trimellitic anhydride) or compounds formed by halogenation of at least one carboxyl group (e.g., trimellitic anhydride chloride).

[0458] In formula (PAI-2), R 111 A 2 R 113 respectively with R in the above formula (2) 111 A 2 R 113 The meanings are the same, and the preferred selection methods are also the same.

[0459] The polyamide-imide precursor may further contain other repeating units.

[0460] Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0461] [Chemical Formula 37]

[0462]

[0463] In formula (PAI-1), R 116R represents a divalent organic group. 111 It represents a divalent organic group.

[0464] In formula (PAI-1), R 116 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0465] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0466] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0467] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms being preferably replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0468] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0469] Moreover, R is preferred 116 Derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0470] In this invention, compounds having two carboxyl groups are referred to as dicarboxylic acid compounds, and compounds having two halogenated carboxyl groups are referred to as dicarboxylic acid dihalides.

[0471] The carboxyl group in a dicarboxylic acid dihalide compound can be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0472] Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides used to manufacture polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0473] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0474] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable to be a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises 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 through single bonds or linking groups.

[0475] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and hexafluoro... Sebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0476] As a specific example of a dicarboxylic acid dihalide compound, a compound with a structure formed by halogenating two carboxyl groups from the above-mentioned specific examples of dicarboxylic acid compounds can be cited.

[0477] In formula (PAI-1), R 111R in equation (2) above 111 The meanings are the same, and the preferred selection methods are also the same.

[0478] Furthermore, the polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0479] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor can 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.

[0480] As one embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

[0481] The polyamide-imide precursor may contain all of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2), or it may contain repeating units represented by formula (PAI-2) and formula (PAI-1) but not the repeating units represented by formula (2), or it may contain repeating units represented by formula (PAI-2) and formula (2) but not the repeating units represented by formula (PA1-1), or it may contain repeating units represented by formula (PA1-2) but not the repeating units represented by formula (PAI-1) and formula (2).

[0482] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited; all repeating units in the polyamide-imide precursor, except for the terminal units, can be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0483] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 1,500 to 500,000, more preferably 1,500 to 100,000, even more preferably 1,500 to 70,000, particularly preferably 5,000 to 70,000, and most preferably 10,000 to 50,000. Furthermore, 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.

[0484] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0485] Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyamide-imide precursors as a single resin are each within the aforementioned ranges.

[0486] [Polyamide-imide]

[0487] The polyamide imide used in this invention can be an alkali-soluble polyamide imide or a polyamide imide soluble in a developer solution with organic solvent as the main component.

[0488] In this specification, alkali-soluble polyamide-imide refers to polyamide-imide in which 0.1 g or more is dissolved in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve 0.5 g or more of polyamide-imide, and more preferably 1.0 g or more of polyamide-imide. There is no particular upper limit to the above-mentioned dissolution amount, but it is preferably 100 g or less.

[0489] Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in the main chain.

[0490] -Fluorine atom-

[0491] From the viewpoint of the membrane strength of the obtained organic membrane, polyamide-imide preferably has fluorine atoms.

[0492] Fluorine atoms are preferably included, for example, in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 .

[0493] The amount of fluorine atoms relative to the total mass of the polyamide imide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0494] -ene unsaturated bond-

[0495] From the perspective of the strength of the obtained organic membrane, polyamide-imide can have olefinically unsaturated bonds.

[0496] Polyamide-imide may have olefinic unsaturated bonds at the end of the main chain or in the side chain, preferably in the side chain.

[0497] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0498] The olefinic unsaturated bond is preferably contained in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 More preferably, R is included as a group having an olefinic unsaturated bond in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 .

[0499] The preferred manner of having groups with olefinic unsaturated bonds is the same as that of having groups with olefinic unsaturated bonds in the polyimide described above.

[0500] The amount of olefinic unsaturated bonds relative to the total mass of polyamide imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0501] -polymeric groups other than olefinic unsaturated bonds-

[0502] Polyamide imides can have polymerizable groups other than olefinic unsaturated bonds.

[0503] As a polymerizable group other than the olefinic unsaturated bond in polyamide-imide, examples can be made of groups that are the same as the polymerizable groups other than the olefinic unsaturated bond in the polyamide-imide described above.

[0504] For example, the polymerizable group other than the olefinic unsaturated bond is preferably included in the repeating unit represented by formula (PAI-3) described later. 111 .

[0505] The amount of polymerizable groups other than olefinic unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0506] -Polar conversion group-

[0507] Polyamide-imides can possess polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyamide-imides interact with the R group in formula (2) above. 113 and R 114 The acid-decomposing groups described in the text are the same, and the preferred methods are also the same.

[0508] -Acid Value-

[0509] When polyamide-imide is used for alkaline development, from the viewpoint of improving developability, the acid value of polyamide-imide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0510] Furthermore, the 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.

[0511] Furthermore, when polyamide-imide is used in development using a developer solution with organic solvent as the main component (e.g., "solvent development" described below), 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.

[0512] The acid value mentioned above is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0513] Furthermore, the acid groups contained in the polyamide imide can be the same as those in the polyimide described above, and the preferred method is also the same.

[0514] -Phenolic hydroxyl-

[0515] From the viewpoint of making the development speed appropriate for alkaline developing solutions, polyamide-imide preferably has phenolic hydroxyl groups.

[0516] Polyamide imides can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0517] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by the formula (PAI-3) described later, in the form of R. 117 or R 111 .

[0518] The amount of phenolic hydroxyl groups relative to the total mass of polyamide imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0519] The polyamide-imide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains repeating units represented by the following formula (PAI-3).

[0520] [Chemical Formula 38]

[0521]

[0522] In formula (PAI-3), R 111 and R 117 respectively with R in equation (PAI-2) 111 and R 117 The meanings are the same, and the preferred selection methods are also the same.

[0523] When it has a polymerizable group, the polymerizable group can be located at R 111 and R 117 At least one of them may also be located at the end of the polyamide imide.

[0524] Furthermore, to improve the storage stability of the resin composition, it is preferable to end the main chain of the polyamide-imide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, or reactive monoester compounds. The preferred methods for using end-capping agents are the same as those for using end-capping agents in the polyimide described above.

[0525] -Imidization rate (ring-closure rate)-

[0526] From the perspective of the obtained organic membrane strength and insulation properties, the imidization rate (also known as "ring-closing rate") of polyamide imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0527] There is no specific upper limit to the imidization rate mentioned above; it can be below 100%.

[0528] The imidization rate described above can be measured using the same method as the ring-closure rate of the polyimide described above.

[0529] Polyamide-imide can have a composition consisting of all 1 type of R111 or R 117 The repeating unit represented by the above formula (PAI-3) can also have R consisting of two or more different kinds. 131 or R 132 The repeating unit represented by the above formula (PAI-3) is used. Furthermore, polyamide-imide may contain other types of repeating units besides the repeating unit represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0530] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method, by fully imidizing it using a known imidization reaction, or by stopping the imidization reaction midway to introduce a partial imide structure, or by introducing a partial imide structure by further mixing the fully imidized polymer with the polyamide-imide precursor.

[0531] The weight-average molecular weight (Mw) of the polyamide-imide is preferably 1,500 to 70,000, more preferably 5,000 to 70,000, even more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight-average molecular weight to 1,500 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or higher.

[0532] 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.

[0533] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0534] Furthermore, when the resin composition contains multiple polyamide-imides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the above-mentioned multiple polyamide-imides are used as a single resin are each within the aforementioned ranges.

[0535] [Methods for manufacturing polyimide precursors, etc.]

[0536] For example, polyimide precursors can be obtained by methods such as: reacting tetracarboxylic dianhydride with diamine at low temperature; reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid and then esterifying it with a condensing agent or alkylating agent; obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred.

[0537] Examples of condensing agents 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.

[0538] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0539] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0540] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0541] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0542] In methods for manufacturing polyimide precursors, a basic compound is preferably added during the reaction. The basic compound can be one type or two or more types.

[0543] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0544] -End- Capping Agent-

[0545] To introduce nitrogen-containing heterocyclic structures with two or more nitrogen atoms as cyclic atoms into a specific resin, for example, end-capping agents can be used.

[0546] For example, by using a compound having a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms and a hydroxyl, thiol, or amino group as a capping agent to cap the carboxylic anhydride and anhydride derivatives at the resin end, it is possible to introduce the structure represented by the above formula (1-1) or formula (2-1) into the end.

[0547] From the viewpoint of reducing the molar amount of the structure containing the nitrogen-containing heterocyclic structure that detaches from the resin during the above heating, it is preferable to use a compound having a nitrogen-containing heterocyclic structure containing two or more nitrogen atoms as cyclic atoms and an amino group as such end-capping agent.

[0548] Furthermore, at this time, other end-capping agents described later can be used simultaneously. From the viewpoint of reducing the molar amount of the structure containing the above-mentioned nitrogen-containing heterocyclic structure that detaches from the resin, it is also preferable not to use other end-capping agents.

[0549] As a compound having a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms and an amino group, for example, a compound represented by the following formula (T-1) can be cited.

[0550] [Chemical Formula 39]

[0551]

[0552] In equation (T-1), L 1 R 1 and n are respectively related to L in the above equation (1-1) 1 R 1 The meanings of 'n' and 'n' are the same, and the preferred selection methods are also the same.

[0553] Furthermore, compounds containing nitrogen-containing heterocyclic structures with two or more nitrogen atoms as cyclic atoms and functional groups capable of reacting with amino groups can be used to cap the amino groups at the ends of resins, thereby introducing the aforementioned nitrogen-containing heterocyclic structures at the ends of specific resins.

[0554] -Other capping agents-

[0555] Examples of such end-capping agents include the following compounds.

[0556] When capping carboxylic anhydrides and their derivatives remaining at the resin ends, end-capping agents include monools, phenols, thiols, thiophene, and monoamines. Considering reactivity and film stability, monools, phenols, and monoamines are preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol (secondary alcohols), tert-butanol, and adamantanol (tertiary alcohols). Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Furthermore, preferred compounds for monoamines 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and various different end groups can be introduced by reacting multiple end-capping agents.

[0557] Furthermore, when capping the amino groups at the resin ends, compounds having functional groups capable of reacting with the amino groups can be used for capping. Preferred capping agents for the amino groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0558] -Solid precipitation-

[0559] The manufacture of polyimide precursors may include a solid precipitation process. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor. To improve the purification degree, the polyimide precursor may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. A further step may be included to remove ionic impurities using an ion exchange resin.

[0560] [Specific example]

[0561] As a specific example of a particular resin, for example, the specific resin used in the embodiments described later can be cited, or a specific resin obtained by changing the end structure of these resins to the structure exemplified in the specific examples of the structure containing the nitrogen-containing heterocyclic structure (which contains two or more nitrogen atoms as cyclic atoms), but is not limited thereto.

[0562] 〔content〕

[0563] The content of a specific resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still even more preferably 95% by mass or less.

[0564] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, the total amount is preferably within the above-mentioned range.

[0565] Furthermore, the resin composition of the present invention preferably contains at least two resins.

[0566] Specifically, the resin composition of the present invention may contain two or more specific resins and other resins described below, or may contain two or more specific resins, preferably two or more specific resins.

[0567] When the resin composition of the present invention contains two or more specific resins, it is preferable, for example, to contain a structure derived from dianhydride (R in formula (2) above). 115 Two or more different polyimide precursors.

[0568] <Other Resins>

[0569] The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0570] Other resins include polyimide precursors different from a specific resin, polyimides different from a specific resin, polybenzoxazole precursors different from a specific resin, polybenzoxazoles different from a specific resin, polyamide-imide precursors different from a specific resin, polyamide-imides different from a specific resin, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc.

[0571] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained.

[0572] For example, by adding (meth)acrylic resin to the resin composition to replace the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. The (meth)acrylic resin has a weight-average molecular weight of 20,000 or less and a high polymerizability value (e.g., the molar amount of polymerizability in 1g of resin is 1×10⁻⁶). -3 (moles / g or higher).

[0573] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition 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.

[0574] 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, relative to the total solid content of the resin composition.

[0575] Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to configure it with a low content of other resins. In the above embodiment, the content of other resins relative to the total solids content of the resin composition 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 still more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0576] 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, the total amount is preferably within the above-mentioned range.

[0577] <Polymerizing compounds>

[0578] The resin composition of the present invention preferably contains a polymerizable compound.

[0579] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0580] [Free radical crosslinking agent]

[0581] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0582] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group contains a group with an olefinic unsaturated bond. Examples of such groups containing an olefinic unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido groups.

[0583] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred groups containing olefinic unsaturated bonds, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0584] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0585] As for the above-mentioned compounds having two or more olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0586] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two olefinic unsaturated bonds and the above-mentioned compound having three or more olefinic unsaturated bonds.

[0587] The molecular weight of the free 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 free radical crosslinking agent is preferably 100 or more.

[0588] Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyols, and amides of unsaturated carboxylic acids and polyvalent amines. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Moreover, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are even more preferred. Furthermore, as other examples, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers can be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0589] Furthermore, the free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. 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, glycerol, or trimethylolethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate addition. Esterified compounds, urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid, and other polyfunctional acrylates or methacrylates; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are preferred. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and olefinic unsaturated bonds, such as glycidyl (meth)acrylate, can also be cited.

[0590] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a fluorene ring and having two or more groups having olefinic unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0591] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, etc., can also be used. Moreover, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0592] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 are also preferred to be used, and these contents are incorporated in this specification.

[0593] Furthermore, the compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) along with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by esterification of (meth)acrylates after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0594] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and this information is incorporated into this specification.

[0595] Preferred free 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 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 Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0596] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four vinyl groups) and SR-209, 231, and 239 (a difunctional methacrylate with four vinyl groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentylene groups) and TPA-330 (a trifunctional acrylate with three isobutylene groups) manufactured by Nippon Kayaku Co., Ltd.; urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300; UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku). (manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

[0597] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Furthermore, compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as free radical crosslinking agents.

[0598] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent with acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that reacts a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxy compound to give it an acid group. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol, in the free radical crosslinking agent that reacts a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxy compound to give it an acid group. Examples of commercially available products include polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0599] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1–300 mg KOH / g, particularly preferably 1–100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent workability during manufacturing, and consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid values ​​were measured according to the description in JIS K 0070:1992.

[0600] From the viewpoint of pattern resolution and film stretchability, the resin composition preferably uses difunctional methacrylates or acrylates.

[0601] As specific compounds, 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-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Dimethacrylates, including dimethylol-tricyclodecane dimethacrylates, dimethylol-tricyclodecane dimethacrylates, ethylene oxide (EO) adduct dimethacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified dimethacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0602] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0603] From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are 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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds with a boiling point of 100°C or higher at atmospheric pressure are also preferred.

[0604] In addition, examples of allyl compounds, such as diallyl phthalate and triallyl trimellitate, can be cited as free radical crosslinking agents with two or more functions.

[0605] When a free radical crosslinking agent is included, its content relative to the total solids content of the resin composition of the present invention is preferably more than 0% by mass and less than 60% by mass. 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.

[0606] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more, their combined dosage is preferably within the range mentioned above.

[0607] [Other crosslinking agents]

[0608] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0609] In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by photosensitization by the aforementioned photoacid generator or photobase generator. More preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by the action of acids or bases.

[0610] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0611] As other crosslinking agents, compounds having at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0612] Other crosslinking agents include, for example, compounds having the following structure: obtained by reacting formaldehyde or formaldehyde and an alcohol with amino-containing compounds such as melamine, acetylacetonate, urea, alkylene urea, and benzoguanamine, and replacing the hydrogen atoms of the aforementioned amino groups with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, these compounds can be oligomers formed by the self-condensation of the hydroxymethyl groups of each other.

[0613] As for the aforementioned amino-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenide, 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 benzoguanidine are called benzoguanidine-based crosslinking agents.

[0614] The resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.

[0615] As a compound containing at least one of alkoxymethyl and acylmethyl groups in this invention, examples of compounds in which the alkoxymethyl or acylmethyl group is directly substituted on an aromatic group, a nitrogen atom of a urea structure described below, or a triazine are provided.

[0616] The alkoxymethyl or acylmethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.

[0617] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0618] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0619] [Chemical Formula 40]

[0620]

[0621] R 100 Indicates alkyl or acyl groups.

[0622] R 101 and R 102 Each of these groups independently represents a monovalent organic group and can bond with each other to form a ring.

[0623] Compounds in which alkoxymethyl or acylmethyl groups are directly substituted on an aromatic group include, for example, compounds of the following general formula.

[0624] [Chemical Formula 41]

[0625]

[0626] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 This refers to a group that represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to form a base-soluble group (e.g., a group that is released by the action of an acid, or a group formed by -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5 This indicates a group that is released by the action of an acid.

[0627] R 105 Each can independently represent an alkyl or alkenyl group, where a, b, and c are each 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.

[0628] Regarding groups that decompose under the action of acid to generate alkali-soluble groups, groups that are released under the action of acid, and groups derived from -C(R) 4 )2COOR 5 The R in the indicated group 5 For example, one can cite -C(R) 36 (R) 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (0R) 39 )wait.

[0629] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0630] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0631] The aforementioned alkyl groups can be either straight-chain or branched.

[0632] As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

[0633] The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as fused rings.

[0634] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0635] As the aforementioned aralkyl group, aralkyl groups with 7 to 20 carbon atoms are preferred, and aralkyl groups with 7 to 16 carbon atoms are more preferred.

[0636] The aryl group mentioned above refers to an aryl group that has been substituted with an alkyl group. The preferred methods for these alkyl and aryl groups are the same as those for the alkyl and aryl groups mentioned above.

[0637] The alkenyl group is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0638] Moreover, these groups can further have known substituents within the scope of achieving the effects of the present invention.

[0639] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0640] The preferred groups, such as tertiary alkyl esters, acetals, cumyl esters, and enols, are those that decompose under acidic conditions to form alkali-soluble groups or are released by acidic conditions. Tertiary alkyl esters and acetals are more preferred.

[0641] As compounds having an alkoxymethyl group, specific examples include the following structures. Compounds having an acylmethyl group include those in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group. As compounds having an alkoxymethyl group or an acylmethyl group intramolecularly, the following compounds can be cited, but are not limited to these.

[0642] [Chemical Formula 42]

[0643]

[0644] [Chemical Formula 43]

[0645]

[0646] Compounds containing at least one of alkoxymethyl and acylmethyl groups can be commercially available or synthesized by known methods.

[0647] From the viewpoint of heat resistance, compounds in which alkoxymethyl or acylmethyl groups are directly substituted on the aromatic ring or triazine ring are preferred.

[0648] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0649] Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylenoid, dihydroxymethylated acetylenoid, trihydroxymethylated acetylenoid, tetrahydroxymethylated acetylenoid, monomethoxymethylated acetylenoid, dimethoxymethylated acetylenoid, trimethoxymethylated acetylenoid, tetramethoxymethylated acetylenoid, monoethoxymethylated acetylenoid, diethoxymethylated acetylenoid, triethoxymethylated acetylenoid, tetraethoxymethylated acetylenoid, monopropoxymethylated acetylenoid, dipropoxymethylated acetylenoid, tripropoxymethylated acetylenoid, tetrapropoxymethylated acetylenoid, monobutoxymethylated acetylenoid, dibutoxymethylated acetylenoid, tributoxymethylated acetylenoid, or tetrabutoxymethylated acetylenoid, etc.

[0650] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0651] Monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc., are vinylurea-based crosslinking agents.

[0652] Acrylurea crosslinking agents such as monohydroxymethylated acrylate, dihydroxymethylated acrylate, monomethoxymethylated acrylate, dimethoxymethylated acrylate, monoethoxymethylated acrylate, diethoxymethylated acrylate, monopropoxymethylated acrylate, dipropoxymethylated acrylate, monobutoxymethylated acrylate, or dibutoxymethylated acrylate.

[0653] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0654] Specific examples of benzoguanidine-based crosslinking agents include, for instance, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0655] Furthermore, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring).

[0656] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0657] Other crosslinking agents can be commercially available products. Preferred commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALACMW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[0658] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from epoxy compounds, oxetane compounds and benzoxazine compounds as other crosslinking agents.

[0659] -Epoxy compounds (compounds containing epoxy groups)-

[0660] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0661] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with two or more repeating units, preferably 2 to 15.

[0662] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones containing epoxy groups such as polymethyl(epoxypropoxypropyl)siloxane, but these are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemmical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKACORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel). The following compounds are manufactured by Nippon Kayaku Co., Ltd.: NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade names, manufactured by Nippon Kayaku Co., Ltd.). Furthermore, the following compounds are also preferred.

[0663] [Chemical Formula 44]

[0664]

[0665] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0666] In the above structure, considering both heat resistance and improved elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[0667] -Oxycyclic butane compounds (compounds containing an oxycyclic butyl group)-

[0668] 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-oxetane-butyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane-butyl)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. is preferred; these can be used alone or in mixtures of two or more.

[0669] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0670] Benzooxazine compounds are preferred because the cross-linking reaction caused by the ring-opening addition reaction does not cause degassing during curing, thereby reducing thermal shrinkage and inhibiting warping.

[0671] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and dihydrobenzoxazine compounds of phenolic varnish type. These can be used alone or in combination of two or more.

[0672] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention 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. Other crosslinking agents may be present in only one type or in two or more types. When two or more other crosslinking agents are present, their total content is preferably within the above-mentioned range.

[0673] [Polymerization initiator]

[0674] The resin compositions of the present invention preferably contain a polymerization initiator capable of polymerization initiated by light and / or heat. Particularly preferred are photopolymerization initiators.

[0675] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are sensitive to light in the ultraviolet to visible regions are preferred. Furthermore, it can be an active agent that interacts with the photoexcited sensitizer to generate active free radicals.

[0676] The photoradical polymerization initiator preferably contains at least one initiator with a molar absorptivity of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of the compound can be measured using known methods. For example, it is preferably measured using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0677] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application 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 Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, 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 Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0678] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application 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 preferred.

[0679] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0680] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGMresins 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.

[0681] 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.

[0682] As an aminoacetophenone initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which match the maximum absorption wavelength to a light source of wavelengths such as 365 nm or 405 nm, can also be used, as this specification is included.

[0683] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.

[0684] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0685] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude and also act as photocuring accelerators.

[0686] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0687] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy(imino))but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In the resin compositions of the present invention, oxime compounds (oxime-based photoradical polymerization initiators) are particularly preferred as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0688] [Chemical Formula 45]

[0689]

[0690] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Moreover, oxime compounds with the following structures can also be used.

[0691] [Chemical Formula 46]

[0692]

[0693] Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Application Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the contents of which are incorporated herein by reference.

[0694] As photoradical polymerization initiators, oxime compounds with at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0695] Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, the contents of which are incorporated herein by reference.

[0696] Nitro-containing oxime compounds can be used as photopolymerization initiators. Nitro-containing oxime compounds are preferably dimers. Specific examples of nitro-containing oxime compounds include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is another example of a nitro-containing oxime compound.

[0697] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0698] As photoradical polymerization initiators, oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0699] As a photopolymerization initiator, it is also possible to use aromatic cyclic groups Ar with electron-withdrawing groups introduced into the aromatic ring. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acyl and nitro groups being preferred. Acyl groups are more preferred for their ability to readily form films with excellent lightfastness, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino groups. More preferred are alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, arylthioalkyl, or amino groups, and even more preferred are alkoxy, alkylthioalkyl, or amino groups.

[0700] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compounds represented by formula (OX2).

[0701] [Chemical Formula 47]

[0702]

[0703] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonyl, carbamoyl, or aminosulfonyl.

[0704] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0705] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0706] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0707] In the above formula, R is preferred. X12 It is an electron-withdrawing group and R X10 R X11 R X13 R X14 It is a hydrogen atom.

[0708] As a specific example of the oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, which is incorporated herein by reference.

[0709] Examples of preferred oxime compounds include those with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0710] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0711] More preferably, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is selected from at least one compound among trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. Even more preferably, it is a metallocene compound or an oxime compound.

[0712] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones that undergo ring condensation with aromatic rings such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyl dimethyl ketal. Moreover, compounds represented by the following formula (I) can also be used.

[0713] [Chemical Formula 48]

[0714]

[0715] In equation (I), R I00The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy group having 1 to 12 carbon atoms, the phenyl group, or the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the halogen atom, the cyclopentyl group, the cyclohexyl group, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are substituted with at least one phenyl or biphenyl group. I01 For groups represented by formula (II) or with R I00 The same group, R I02 ~R I04 Each is independently an alkyl group, an alkoxy group, or a halogen atom with 1 to 12 carbon atoms.

[0716] [Chemical Formula 49]

[0717]

[0718] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0719] Furthermore, the photoradical polymerization initiator can also use compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which is incorporated in this specification.

[0720] As photoradical polymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Moreover, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc., are included in this specification.

[0721] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention 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. The photopolymerization initiator may be only one type or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0722] In addition, photopolymerization initiators can sometimes also function as thermal polymerization initiators. Therefore, heating with ovens, heating plates, etc., can further promote crosslinking based on photopolymerization initiators.

[0723] [Sensitizer]

[0724] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0725] As usable sensitizers, compounds such as benzophenone, mifepristone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0726] Examples of sensitizers include mifepristone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminophenylenepropyl dihydroindone. Aminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0727] Furthermore, other sensitizing pigments can also be used.

[0728] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0729] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition 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. A single sensitizer may be used alone, or two or more may be used in combination.

[0730] [Chain transfer agent]

[0731] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, RiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferred.

[0732] Furthermore, the chain transfer agent can also use compounds described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0733] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total amount is preferably within the above-mentioned range.

[0734] [Photoacid generator]

[0735] The resin composition of the present invention preferably contains a photoacid generator.

[0736] A photoacid generator is a compound that produces at least one of Brønsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator capable of generating acid through photosensitivity is preferred.

[0737] Examples of acids that can be produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0738] Examples of photoacid generating agents used in the resin compositions of the present invention include, for example, quinone diazide compounds, oxime sulfonate compounds, organohalogenated compounds, organoborate compounds, disulfone compounds, onium salt compounds, etc.

[0739] From the perspective of sensitivity and storage stability, organic halogen compounds, oxime sulfonates, and onium salts are preferred. From the perspective of the mechanical properties of the formed membrane, oxime esters are preferred.

[0740] Examples of quinone diazide compounds include compounds in which the sulfonic acid of quinone diazide is bonded to a mono- or poly-hydroxy compound via an ester bond; compounds in which the sulfonic acid of quinone diazide is bonded to a mono- or poly-amino compound via a sulfonamide bond; and compounds in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy or polyamino compound via an ester bond and / or a sulfonamide bond. These polyhydroxy, polyamino, and polyhydroxy polyamino compounds do not require all functional groups to be replaced by quinone diazide, but preferably, at least 40 mol% of the total functional groups are replaced by quinone diazide on average. By containing such quinone diazide compounds, resin compositions sensitive to general ultraviolet light, i.e., i.e., i.e., mercury lamp i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm), can be obtained.

[0741] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, and 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, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, Honshu Chemical Industry The products include, but are not limited to, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc.

[0742] As amino compounds, examples include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylene diamine, 1,3-phenylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, etc., but are not limited to these.

[0743] Moreover, examples of polyhydroxy polyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but these are not limited to.

[0744] Among them, the preferred esters, which contain a phenolic compound and a 4-naphthoquinone diazidesulfonyl group, are quinone diazidesulfonyl compounds. This allows for higher sensitivity and higher resolution during I-ray exposure.

[0745] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, a comparison between the exposed and unexposed portions can be obtained, thereby achieving high sensitivity, which is therefore preferred. Sensitizers, etc., can be further added as needed.

[0746] The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound").

[0747] There are no particular limitations on the presence of an oxime sulfonate group in the oxime sulfonate compound, but oxime sulfonate compounds represented by the following formula (OS-1), the formula described later (OS-103), the formula (OS-104) or the formula (OS-105) are preferred.

[0748] [Chemical Formula 50]

[0749]

[0750] In equation (OS-1), X 3 Represents an alkyl, alkoxy, or halogen atom. X 3 When multiple instances exist, they can be the same or different. The aforementioned X... 3 The alkyl and alkoxy groups in X may have substituents. As described above, X... 3 The alkyl group in the text is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. As described above, X... 3 The alkoxy group in the above-mentioned X is preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in it is preferably a chlorine atom or a fluorine atom.

[0751] In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 They can be the same or different.

[0752] In equation (0S-1), R 34The symbol represents an alkyl or aryl group, preferably an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 5 carbon atoms, a haloalkoxy group with 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 5 carbon atoms, or a haloalkoxy group with 1 to 5 carbon atoms, an aryl group with 6 to 20 carbon atoms, or a haloaryl group with 6 to 20 carbon atoms.

[0753] In equation (0S-1), m3 is 3, X 3 Methyl, X 3 The replacement position is adjacent, R 34 Especially preferred are compounds with straight-chain alkyl groups having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorborneolmethyl, or p-tolyl groups.

[0754] Specific examples of oxime sulfonate compounds represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674, which are incorporated herein by reference.

[0755] [Chemical Formula 51]

[0756]

[0757] In equations (OS-103) to (OS-105), R s1 R indicates alkyl, aryl, or heteroaryl. s2 When multiple atoms are present, they each independently represent a hydrogen atom, alkyl group, aryl group, or halogen atom, R. s6 When multiple groups exist, they independently represent halogen atoms, alkyl groups, alkoxy groups, sulfonic acid groups, aminosulfonyl groups, or alkoxysulfonyl groups, with Xs representing O or S, ns representing 1 or 2, and ms representing integers from 0 to 6.

[0758] In equations (OS-103) to (OS-105), R s1 The alkyl (preferably 1 to 30 carbon atoms), aryl (preferably 6 to 30 carbon atoms), or heteroaryl (preferably 4 to 30 carbon atoms) indicated may have known substituents within the range of achieving the effects of the present invention.

[0759] In formula (OS-103) to formula (OS-105), R s2 Preferably, it is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. s2When two or more atoms are present in the compound, it is preferable that one or two of them are alkyl, aryl, or halogen atoms, more preferably one is an alkyl, aryl, or halogen atom, and particularly preferably one is an alkyl atom and the rest are hydrogen atoms. (From R) s2 The alkyl or aryl groups represented may have known substituents within the range of achieving the effects of the present invention.

[0760] In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, preferably O. In formulas (OS-103) to (OS-105) above, the ring containing Xs as a cyclic atom is a 5-membered ring or a 6-membered ring.

[0761] In formulas (OS-103) to (OS-105), ns represents 1 or 2. Preferably, ns is 1 when Xs is 0, and preferably ns is 2 when Xs is S.

[0762] In equations (OS-103) to (OS-105), R s6 The alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) may have substituents.

[0763] In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and especially preferably 0.

[0764] Furthermore, compounds represented by the above formula (OS-103) are particularly preferred to be compounds represented by the following formulas (OS-106), (OS-110), or (OS-111); compounds represented by the above formula (OS-104) are particularly preferred to be compounds represented by the following formula (OS-107); and compounds represented by the above formula (OS-105) are particularly preferred to be compounds represented by the following formulas (OS-108) or (OS-109).

[0765] [Chemical Formula 52]

[0766]

[0767] In formula (OS-106) to formula (OS-111), R t1 R indicates alkyl, aryl, or heteroaryl. t7 R represents a hydrogen atom or a bromine atom. t8 Represents hydrogen atoms, alkyl groups with 1 to 8 carbon atoms, halogen atoms, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl, R t9 R represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group. t2 It represents a hydrogen atom or a methyl group.

[0768] In formula (OS-106) to formula (OS-111), R t7 It represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

[0769] In formula (OS-106) to formula (OS-111), R t8 The atom 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, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and especially preferably a methyl group.

[0770] In formula (OS-106) to formula (OS-111), R t9 It represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom.

[0771] R t2 It represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0772] Moreover, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be any one or a mixture.

[0773] Specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0774] As another preferred form of oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formulas (OS-101) and (OS-102) are examples.

[0775] [Chemical Formula 53]

[0776]

[0777] In formula (OS-101) or formula (OS-102), R u9 This indicates a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acyl, carbamoyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. More preferably, R. u9 In the form of cyano or aryl, R is further preferred. u9 It can be in the form of cyano, phenyl, or naphthyl.

[0778] In formula (OS-101) or formula (OS-102), R u2a Indicates alkyl or aryl.

[0779] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR. u5 -, -CH2-, -CR u6 H- or CR u6 R u7 -, R u5 ~R u7 Each can be represented independently as either alkyl or aryl.

[0780] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these groups 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 sulfonyl group, a cyano group, or an aryl group. R u1 ~R u4 The two atoms in the ring can bond to each other to form a ring. At this point, the ring can condense and form a fused ring together with the benzene ring. As R... u1 ~R u4 Preferably, hydrogen atoms, halogen atoms, or alkyl groups are used, and R is also preferred. u1 ~R u4 The aryl group is formed by at least two of the molecules bonding with each other. Preferably, R... u1 ~R u4 All of these are hydrogen atoms. All of the above substituents can be further substituented.

[0781] The compound represented by the above formula (OS-101) is more preferably the compound represented by formula (OS-102).

[0782] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be either one or a mixture.

[0783] Specific examples of compounds represented by formula (OS-101) include compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, which are incorporated herein by reference.

[0784] Of the above compounds, b-9, b-16, b-31, and b-33 are preferred.

[0785] [Chemical Formula 54]

[0786]

[0787] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pute Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0788] Furthermore, as a preferred example, compounds represented by the following structural formulas can also be cited.

[0789] [Chemical Formula 55]

[0790]

[0791] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42,2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". Compounds described in Chemistry 1 (No. 3), (1970), etc., are incorporated herein by reference. In particular, as preferred examples, trihalomethyl-substituted oxazole compounds, such as triazine compounds, are cited.

[0792] More preferably, a triazine derivative having at least one mono, di, or trihalogen-substituted methyl group bonded to the triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-triazine, 2,4,6-tris(dichloromethyl)-triazine, 2,4,6-tris(trichloromethyl)-triazine, 2-methyl-4,6-bis(trichloromethyl)-triazine, 2-n-butyl-4,6-bis(trichloromethyl)-triazine, 2- (α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-triazine, 2-phenyl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-triazine, 2-[1-(p-methoxyphenyl) [2,4-Butadienyl]-4,6-bis(trichloromethyl)-triazine, 2-styryl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-naphthoxy) Naphthalene-4,6-bis(trichloromethyl)-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-triazine, 2,4,6-tris(dibromomethyl)-triazine, 2,4,6-tris(tribromomethyl)-triazine, 2-methyl-4,6-bis(tribromomethyl)-triazine, 2-methoxy-4,6-bis(tribromomethyl)-triazine, etc.

[0793] As organoborate compounds, examples include, for instance, Japanese Patent Application Publication No. 62-143044, Japanese Patent Application Publication No. 62-150242, Japanese Patent Application Publication No. 9-188685, Japanese Patent Application Publication No. 9-188686, Japanese Patent Application Publication No. 9-188710, Japanese Patent Application Publication No. 2000-131837, Japanese Patent Application Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Publication No. 2002-116539, and Kunz, Martin, “Rad Tech’98. Proceeding April”. Organoborates described in publications such as "Chicago" (19-22, 1998), organoboron sulfonium complexes or organoboron oxysulfonium complexes described in Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and organoboron iodine complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553. The contents of this specification include complexes, organoboron-phosphorus complexes disclosed in Japanese Patent Application Publication No. 9-188710, organoboron transition metal coordination complexes disclosed in Japanese Patent Application Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014.

[0794] Examples of disulfone compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2001-132318, as well as diazonium disulfone compounds.

[0795] Examples of the aforementioned onium salt compounds include, for instance, diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980); ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; phosphate salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; European Patent Nos. 104,143, 339,049, and 410,201; iodine salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and European Patent Nos. 370,693 and 39... The matte salts described in the specifications of U.S. Patent No. 0,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, and JVCrivello, are... The selenium salts described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), and the arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) are included in this specification.

[0796] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III).

[0797] [Chemical Formula 56]

[0798]

[0799] In formula (RI-I), Ar 11The term "aryl group" refers to an aryl group having 1 to 6 substituents and having 20 or fewer carbon atoms. Preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 2 to 12 carbon atoms, alkylamide groups with 1 to 12 carbon atoms in alkyl groups, or arylamide groups with 6 to 20 carbon atoms in aryl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. 11 The terms represent monovalent anions, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. From a stability perspective, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar... 21 Ar 22 Each of the substituents can independently represent an aryl group having 1 to 6 substituents and a carbon number of 1 to 20. 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, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups with alkyl groups having 1 to 12 carbon atoms, alkylamide groups or arylamide groups with alkyl groups having 1 to 12 carbon atoms, 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. 21 - The term represents a monovalent anion, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering 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 33Each can independently represent an aryl or alkyl, alkenyl, or alkynyl group having 1 to 6 substituents and 6 to 20 carbon atoms. Aryl groups are preferred in terms of reactivity and stability. Preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups with 1 to 12 carbon atoms in each alkyl group, carbonyl, carboxyl, cyano, sulfonyl, thioalkyl, and thioaryl groups with 1 to 12 carbon atoms. 31 The term represents monovalent anions, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

[0800] The following are specific examples of preferred photoacid generators.

[0801] [Chemical Formula 57]

[0802]

[0803] [Chemical Formula 58]

[0804]

[0805] [Chemical Formula 59]

[0806]

[0807] [Chemical Formula 60]

[0808]

[0809] [Chemical Formula 61]

[0810]

[0811] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, even more preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass.

[0812] A single photoacid generator can be used alone, or multiple generators can be used in combination. When multiple generators are used in combination, the total amount of these generators is preferably within the range mentioned above.

[0813] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0814] <Alkali-generating agents>

[0815] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents for the resin composition of the present invention include thermal alkali-generating agents and photo-alkali-generating agents.

[0816] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, thereby improving the mechanical properties and chemical resistance of the cured product, and improving the performance of, for example, the interlayer insulating film used as a rewiring layer in semiconductor packaging.

[0817] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from the base-generating agent include, for example, secondary and tertiary amines.

[0818] There are no particular limitations on the alkali-generating agents involved in this invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0819] Specific compounds that can be cited as nonionic base generating agents include those represented by formula (B1), formula (B2), or formula (B3).

[0820] [Chemical Formula 62]

[0821]

[0822] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2and Rb 3 None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, it is not limited to this definition when the bonded carbon atoms are carbon atoms that form a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0823] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, more preferably at least two rings. The cyclic structure can be any of a monocyclic or fused ring, preferably a monocyclic or a fused ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0824] More specifically, Rb 1 and Rb 2 Preferably, the groups are hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl groups (preferably with 2 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), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). These groups may have substituents within the range that enables the effects of the present invention. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are 4- to 7-membered nitrogen-containing heterocycles. In particular, Rb... 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0825] As Rb 3Examples of such compounds 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), aralkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), areneyl 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 aralkoxy 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 3 to 18, and even more preferably 3 to 12), arylyl groups, and aralkoxy groups are preferred. Rb 3 The invention may further contain substituents within the scope of achieving the effects of the invention.

[0826] The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

[0827] [Chemical Formula 63]

[0828]

[0829] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 They have the same meaning.

[0830] Rb 13 The groups are alkyl (preferably 1-24 carbon atoms, more preferably 2-18, even more preferably 3-12), alkenyl (preferably 2-24 carbon atoms, more preferably 2-18, even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, even more preferably 6-12), or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, even more preferably 7-12), and may have substituents within the range that allows the effects of the present invention to be achieved. Rb 13 Preferably, it is an aryl alkyl group.

[0831] Rb 33 and Rb 34Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0832] Rb 35 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), with aryl being the most preferred.

[0833] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0834] [Chemical Formula 64]

[0835]

[0836] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 They have the same meaning.

[0837] Rb 15 and Rb 16 The atom is hydrogen, alkyl (preferably 1-12 carbon atoms, more preferably 1-6, even more preferably 1-3), alkenyl (preferably 2-12 carbon atoms, more preferably 2-6, even more preferably 2-3), aryl (preferably 6-22 carbon atoms, more preferably 6-18, even more preferably 6-10), aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, even more preferably 7-11), and preferably hydrogen or methyl.

[0838] Rb 17 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), with aryl being the most preferred.

[0839] [Chemical Formula 65]

[0840]

[0841] In formula (B3), L represents a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the path of the linking chain. Furthermore, R... N1 and R N2 Each can be used to represent a monovalent organic group independently.

[0842] In this specification, a "linking chain" refers to an atomic chain along a path that links two atoms or groups of atoms of the linked objects, with the shortest (minimum number of atoms) distance between them. For example, in a compound represented by the following formula, L is composed of styrene, has vinyl as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms along the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0843] [Chemical Formula 66]

[0844]

[0845] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and especially preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of enabling the intramolecular cyclization reaction to proceed rapidly, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds as base generating agents 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.

[0846] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0847] [Chemical Formula 67]

[0848]

[0849] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0850] 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. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0851] In equation (N1), R N1 and R N2 Each of these groups 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), 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 aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with aliphatic hydrocarbon groups being preferred. As R N1 and R N2 If an aliphatic hydrocarbon group is used, the resulting base has high basicity, which is therefore preferred. Furthermore, the aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can also have oxygen atoms in the substituents within the aliphatic hydrocarbon chain or the aromatic ring. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms within the hydrocarbon chain.

[0852] As a component of R N1 and R N2 The aliphatic hydrocarbon group can be exemplified by straight-chain or branched chain alkyl groups, cyclic alkyl groups, combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. The straight-chain or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0853] Cyclic alkyl groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0854] The group involved in the combination of chain alkyl and cyclic alkyl groups preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the groups involved in the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0855] The alkyl group containing oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group containing oxygen atoms in the chain can be chain-like or cyclic, and can also be straight-chain or branched.

[0856] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, the alkyl group has 5 to 12 carbon atoms. In formulations where adhesion to metal (e.g., copper) layers is important, groups having cyclic alkyl groups and alkyl groups having 1 to 8 carbon atoms are preferred.

[0857] R N1 and R N2 They can link together to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, R... N1 and R N2 The formed ring structure can be a monocyclic ring or a fused ring, with a monocyclic ring being preferred. The formed ring structure is preferably a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1), such as pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleidine rings, piperidine rings, piperazine rings, and morpholine rings being particularly preferred.

[0858] R C1 This indicates a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0859] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0860] Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxacyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP)yl.

[0861] The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that can have an oxygen atom in the chain is preferred, more preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that can have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group that can have an oxygen atom in the chain. These groups preferably do not have oxygen atoms.

[0862] 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 involved in the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (e.g., arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0863] As the linking group L, specifically, preferably a linear or branched alkylene group, a cyclic alkylene group, a combination of linear and cyclic alkylene groups, an alkylene group having an oxygen atom in the chain, a linear or branched alkenyl group, a cyclic alkenyl group, an aryl group, or an aryl alkylene group.

[0864] The linear or branched alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

[0865] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0866] The combination of chain-like and cyclic-like alkylene groups preferably involves groups with 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6.

[0867] The alkylene group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. Preferably, the alkylene group containing oxygen atoms in the chain has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

[0868] The linear or branched chain-like alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain-like alkenyl group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3.

[0869] The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenyl group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2.

[0870] The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10.

[0871] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0872] Preferably, the compounds are chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, arylene, and arylene alkylene; more preferably, 1,2-vinyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and vinyloxyvinyl (especially 1,2-vinyloxy-1,2-vinyl).

[0873] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting thereto.

[0874] [Chemical Formula 68]

[0875]

[0876] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0877] Specific examples of preferred compounds as ionic base generators include, for instance, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0878] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[0879] [Chemical Formula 69]

[0880]

[0881] Specific examples of imine salts include the following compounds, but the present invention is not limited to these.

[0882] [Chemical Formula 70]

[0883]

[0884] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of resin in the resin composition of the present invention is preferably 0.1 to 50 parts by weight. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, or 5 parts by weight or less, or even 4 parts by weight or less.

[0885] One or more alkali-generating agents can be used. When two or more are used, the total dosage is preferably within the range mentioned above.

[0886] Solvent

[0887] The resin composition of the present invention preferably contains a solvent.

[0888] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0889] Examples of esters preferably 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, 6-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.)). Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-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-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0890] Examples of 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 dimethyl 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.

[0891] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0892] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0893] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0894] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0895] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0896] 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, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0897] From the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvent forms.

[0898] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydroL-glucanone, or a mixture of two or more solvents, is preferred. Particularly preferred are the combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate.

[0899] Regarding the solvent content, from the viewpoint of coatability, it is preferable to set the total solids concentration of the resin composition of the present invention to be 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 required thickness of the coating and the coating method.

[0900] The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, their total amount is preferably within the range described above.

[0901] <Metal Adhesion Modifier>

[0902] The resin composition of the present invention preferably contains a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0903] [Silane coupling agent]

[0904] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, all of which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Moreover, the following compounds are preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0905] [Chemical Formula 71]

[0906]

[0907] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyl... 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0908] [Aluminum-based adhesive additives]

[0909] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0910] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are included in this specification.

[0911] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes better; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become better. The metal adhesion modifier can be only one type or two or more types. When two or more types are used, their total content is preferably within the above range.

[0912] <Migration Inhibitors>

[0913] The resin composition of the present invention may further contain migration inhibitors.

[0914] Compounds belonging to the specific resins mentioned above are not considered migration inhibitors.

[0915] By including migration inhibitors, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0916] There are no particular limitations on the types of compounds that can be used as migration inhibitors. Examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds with thiourea and thioalkyl groups, hindered phenolic compounds, salicylic acid derivatives, and hydrazide derivatives. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0917] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0918] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0919] Furthermore, as a migration inhibitor, it may contain nitrogen-containing compounds that contain a nitrogen-containing heterocycle and an amino group in the same compound, wherein one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms of the cyclizing atom of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

[0920] In the aforementioned nitrogen-containing compounds, preferably at least one of the nitrogen atoms, which are cyclic atoms, is directly bonded to the carbonyl group.

[0921] By including such compounds, it is sometimes possible to further improve the adhesion of the metal to the cured film after a long period of time.

[0922] The following compounds can be cited as specific examples of migration inhibitors.

[0923] [Chemical Formula 72]

[0924]

[0925] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solids content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0926] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range mentioned above.

[0927] <Polymerization Inhibitor>

[0928] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0929] Preferred compounds as polymerization inhibitors 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-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and 1-nitroso-2-naphthyl Phenol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-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-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenothiazine, phenazine, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, it is possible to use the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Patent Application Publication No. 2015 / 125469, the contents of which are incorporated in this specification.

[0930] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition of the present invention 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.

[0931] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, their total number is preferably within the range mentioned above.

[0932] Acid scavenger

[0933] To reduce changes in performance over time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Here, an acid scavenger is a compound that can capture the generated acid by being present in the system, and preferably a compound with low acidity and high pKa. As an acid scavenger, compounds having an amino group are preferred, including primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc., and more preferably primary amines, secondary amines, tertiary amines, and ammonium salts.

[0934] Preferred acid scavengers include compounds having imidazole, diazabicyclic, ononium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and / or ether bonds; and aniline derivatives having hydroxyl and / or ether bonds. When having an ononium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodine, sulfonium, phosphorus, pyridinium, etc., and an anion of an acid with a lower acidity than the acid generated by the acid generator.

[0935] Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers with a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undecyl-7-ene. Examples of acid scavengers with a onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, benzoylmethylsulfonium hydroxide, and sulfonium hydroxides with a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodine hydroxide, benzoylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers with a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and / or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tri(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and / or ether bonds include N,N-bis(hydroxyethyl)aniline.

[0936] Specific examples of preferred acid scavenging agents 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, and N-methylhexylamine. N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexyl, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamine ethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0937] These acid scavengers can be used alone or in combination of two or more.

[0938] The compositions involved in this invention may or may not contain an acid scavenger, but when they do, the content of the acid scavenger is based on the total solid content of the composition, typically 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

[0939] The preferred ratio of acid generator to acid scavenger is an acid generator / acid scavenger molar ratio of 2.5 to 300. That is, considering sensitivity and resolution, a molar ratio of 2.5 or higher is preferred; and considering the problem of resolution degradation due to coarsening of the embossed pattern over time during the post-exposure heat treatment period, a ratio of 300 or lower is preferred. An acid generator / acid scavenger molar ratio is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0940] <Other Additives>

[0941] The resin composition of the present invention can be incorporated with various additives as needed within the range of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the film properties and other properties can be adjusted. Regarding these components, for example, reference can be made to the descriptions after paragraph 0183 of Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, their total amount is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0942] [surfactants]

[0943] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0944] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant composition, the interfacial tension between the coated surface and the coating liquid decreases, improving the wettability of the coated surface and enhancing the coating properties. Therefore, it is possible to further preferably form a film with a uniform thickness and small thickness non-uniformity.

[0945] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novee FC4430, Novee FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASolutions Inc.), etc. Fluorinated surfactants can also use 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, which are included in this specification. As a fluorinated surfactant, block polymers can also be used. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0946] Fluorinated surfactants can also preferably use fluorinated polymers that contain repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups). Examples of fluorinated surfactants that can be used in this invention include the following compounds.

[0947] [Chemical Formula 73]

[0948]

[0949] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0950] Regarding fluorinated surfactants, fluorinated polymers with olefinically unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include 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. Furthermore, commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DICCorporat ion.

[0951] The fluorine content in the fluorinated surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness, liquid saving, and good solubility in the composition.

[0952] Examples of silicone-based surfactants include ToraySilicone DC3PA, ToraySilicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, ToraySilicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-EtsuChemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0953] Examples of hydrocarbon-based surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD).

[0954] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONI C (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., Ltd.), etc.

[0955] As cationic surfactants, examples include organosiloxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers such as POLYFLOW No.75, No.77, No.90, and No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0956] As anionic surfactants, examples include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0957] Surfactants can be used in single-agent or in combination of two or more.

[0958] The surfactant content relative to the total solids content of the composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

[0959] [Higher fatty acid derivatives]

[0960] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the resin composition of the present invention so that they are biased towards the surface of the resin composition of the present invention during the drying process after coating.

[0961] Furthermore, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0962] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative or two or more types. When there are two or more types of higher fatty acid derivatives, their total content is preferably within the above-mentioned range.

[0963] [Thermal polymerization initiator]

[0964] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of polymerizable compounds. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be further advanced, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization by heat, and therefore can sometimes be added as thermal polymerization initiators.

[0965] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be cited as thermal free radical polymerization initiators.

[0966] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention 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. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0967] [Inorganic particles]

[0968] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0969] The average particle size of the aforementioned 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 especially preferably 0.04 to 0.5 μm.

[0970] The above-mentioned average particle size of inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by dynamic light scattering method using a Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0971] If the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0972] [Ultraviolet absorber]

[0973] The compositions of the present invention may contain ultraviolet absorbers. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0974] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. 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-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0975] Examples of acrylonitrile-based ultraviolet absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecoxypropyl)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; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Bis(hydroxyphenyl)triazine compounds such as 4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-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; 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-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine.

[0976] In this invention, the various ultraviolet absorbers mentioned above can be used individually or in combination of two or more.

[0977] The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less.

[0978] [Organotitanium compounds]

[0979] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0980] Examples of usable organotitanium compounds include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0981] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0982] I) Chelated titanium compounds: Among these, chelated titanium compounds having two or more alkoxy groups are more preferred, considering the excellent storage stability of the resin composition and the ability to obtain a good cured pattern. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediate) titanium, and diisopropoxybis(ethyl acetoacetate) titanium.

[0983] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0984] III) Titanium decene compounds: such as pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0985] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0986] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0987] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0988] VII) Titanate coupling agents: such as isopropyltris(2-dodecylbenzenesulfonyl)titanate, etc.

[0989] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the above-mentioned I) chelated titanium compounds, II) tetraalkoxy titanium compounds, and III) diacetic titanium compounds is preferred as the organotitanium compound. In particular, diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

[0990] When an organotitanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the amount incorporated is 0.05 parts by weight or more, the cured pattern obtained more effectively exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the composition exhibits better storage stability.

[0991] [Antioxidants]

[0992] The compositions of the present invention may contain antioxidants. By including antioxidants as additives, the tensile properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds are examples. Compounds having substituents at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. Moreover, phosphorus-based antioxidants are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphahepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphahepta-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants can also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Moreover, the compositions of the present invention may contain potential antioxidants as needed. Compounds that function as potential antioxidants include those whose antioxidant sites are protected by a protecting group, and whose antioxidant properties are detached by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst. Compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are also potential antioxidants, and these are incorporated herein by reference. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0993] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0994] [Chemical Formula 74]

[0995]

[0996] In general formula (3), R 5 R represents an alkyl group having 2 or more hydrogen atoms or carbon atoms (preferably 2 to 10 carbon atoms). 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 It represents a 1- to 4-valent organic group containing at least one of an alkylene group, an oxygen atom, and a nitrogen atom with 2 or more carbon atoms (preferably 2 to 10 carbon atoms). k represents an integer from 1 to 4.

[0997] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups in the resin. Moreover, it can inhibit metal oxidation by preventing rust on metallic materials.

[0998] In order to be effective on both resin and metal materials simultaneously, k is more preferably an integer from 2 to 4. As R 7 Examples of suitable compounds include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and compounds formed by combining these groups. These compounds may further contain substituents. From the viewpoint of solubility in the developer and metal adhesion, compounds containing alkyl ethers or -NH- are preferred; from the viewpoint of metal adhesion resulting from interaction with the resin and the formation of metal complexes, -NH- is more preferred.

[0999] Examples of compounds represented by general formula (3) include the following compounds, but are not limited to the following structures.

[1000] [Chemical Formula 75]

[1001]

[1002] [Chemical Formula 76]

[1003]

[1004] [Chemical Formula 77]

[1005]

[1006] [Chemical Formula 78]

[1007]

[1008] The amount of antioxidant added relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain improved tensile properties and adhesion to metal materials even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, their total amount is preferably within the above-mentioned range.

[1009] [Anticoagulant]

[1010] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[1011] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[1012] The composition of the present invention may or may not contain an anti-coagulant, but when it is contained, the content of the anti-coagulant relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less.

[1013] [Phenolic compounds]

[1014] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORAT[ON]).

[1015] In this invention, phenolic compounds can be used alone or in combination of two or more.

[1016] The compositions of the present invention may or may not contain phenolic compounds, but when they are contained, the content of phenolic compounds relative to the total solid content of the compositions of the present invention is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.

[1017] [Other polymers]

[1018] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modifiers incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[1019] In this invention, other polymer compounds can be used alone or in combination of two or more.

[1020] The composition of the present invention may or may not contain other polymeric compounds, but when it does contain other polymeric compounds, the content of other polymeric compounds relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.

[1021] <Characteristics of Resin Compositions>

[1022] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. Within the above range, it is easy to obtain a coating film with high uniformity. For example, 1,000 mm 2 At speeds above 12,000 mm, it is easy to coat to the required film thickness for use as an insulating film for rewiring. 2 When the speed is below a certain value, a coating film with excellent surface finish can be obtained.

[1023] <Restrictions on substances contained in resin compositions>

[1024] The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. When it is less than 2.0%, the storage stability of the resin composition is improved.

[1025] Methods for maintaining moisture content include adjusting humidity in storage conditions and reducing the porosity of the storage container.

[1026] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above-mentioned range.

[1027] Furthermore, as a method to reduce unintended metallic impurities in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[1028] When considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The amount present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[1029] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[1030] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layer bottles with an inner wall composed of six layers of six different resins, or bottles with a seven-layer structure formed by six different resins, are preferred. Examples of such containers include those described in Japanese Patent Application Publication No. 2015-123351.

[1031] <Cure of the resin composition>

[1032] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1033] The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

[1034] The curing of the resin composition is preferably carried out by heating, more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to applications such as forming a protective film on the wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, and imparting heat dissipation function. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[1035] The shrinkage rate of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated according to the following formula.

[1036] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[1037] <Characteristics of cured resin compositions>

[1038] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[1039] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[1040] The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[1041] <Preparation of Resin Compositions>

[1042] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[1043] Mixing can be carried out by stirring blades, by ball milling, or by rotating the tank itself.

[1044] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1045] Furthermore, for the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration is preferably performed using a filter. Regarding the filter pore size, for example, a pore size of 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is polytetrafluoroethylene, preferably polyethylene or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a pore size of 1 μm can be used as the first stage, and an HDPE filter with a pore size of 0.2 μm can be used as the second stage, and the two can be connected in series. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Furthermore, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure can be 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[1046] Besides using filters for filtration, adsorption materials can also be used for impurity removal. Furthermore, a combination of filter filtration and impurity removal using adsorption materials can be employed. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[1047] After filtration, a further step can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[1048] (Method for manufacturing solidified products)

[1049] The method for manufacturing the cured product of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film.

[1050] Furthermore, the method for manufacturing the cured product of the present invention more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[1051] The method for manufacturing the cured product of the present invention preferably includes at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[1052] Furthermore, the manufacturing method of the present invention preferably includes the above-described film formation step and the step of heating the above-described film.

[1053] The following is a detailed explanation of each process.

[1054] <Membrane Formation Process>

[1055] The resin composition of the present invention can be used in a film forming process suitable for forming a film on a substrate.

[1056] The method for manufacturing the cured product of the...

Claims

1. A resin composition comprising a cyclized resin or a resin as a precursor thereof, The resin contains a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms. The molar amount of the structure containing the nitrogen-containing heterocyclic structure that is separated from the resin by heating it at 1 atmosphere and 350°C for 2 hours is less than 10% of the total molar amount of the nitrogen-containing heterocyclic structure contained in the resin. As the nitrogen-containing heterocyclic structure, the resin comprises a structure represented by formula (1-1) or formula (2-1) at the end of the resin. The resin is selected from at least one resin chosen from polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor. In equation (1-1), L 1 R represents a single bond or an n+1 valent linkage group that does not contain an imide ring structure. 1 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where n represents an integer greater than or equal to 1, and * indicates a bonding site with other structures. In equation (2-1), L 2 R represents a single bond or an m+1 valence linker that does not contain an oxazole ring structure. 2 This indicates a nitrogen-containing heterocyclic structure with two or more nitrogen atoms as cyclic atoms, where m represents an integer greater than 1, and * represents a bonding site with other structures.

2. The resin composition according to claim 1, wherein, The content of nitrogen-containing heterocyclic structures with two or more nitrogen atoms as cyclic atoms is 0.001% to 10% by mass relative to the total solid content of the composition.

3. The resin composition according to claim 1 or 2, wherein, The nitrogen-containing heterocyclic structure contained in the resin includes an imidazole skeleton, a triazole skeleton, or a tetraazole skeleton.

4. The resin composition according to claim 1 or 2, wherein, The weight-average molecular weight of the resin is 1500 to 70000.

5. The resin composition according to claim 1 or 2, used for forming an interlayer insulating film for a rewiring layer.

6. A cured product formed by curing the resin composition according to any one of claims 1 to 5.

7. A laminate comprising two or more layers of the cured material of claim 6, wherein any of the cured materials contain a metal layer between each other.

8. A method for manufacturing a cured material, comprising a film forming step of applying the resin composition of any one of claims 1 to 5 to form a film on a substrate.

9. The method for manufacturing a cured material according to claim 8, comprising an exposure step of exposing the film and a development step of developing the film.

10. The method for manufacturing a cured product according to claim 8, comprising a heating step of heating the film at 50°C to 450°C.

11. A semiconductor device comprising the cured material of claim 6.

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