Resin compositions, cured products, laminates, methods for manufacturing cured products and semiconductor devices, and precursors of cyclized resins

Abstract

The present invention provides a resin composition, a cured product obtained by curing the resin composition, a laminate containing the cured product, a semiconductor device containing the cured product or the laminate, a method for manufacturing the cured product that can obtain a cured product with excellent rectangularity, and a precursor of a novel cyclized resin, wherein the resin composition contains a precursor of a cyclized resin, and the precursor of the cyclized resin is a precursor of a cyclized resin that generates alkali when heated to 250°C.

Description

Technical Field

[0001] This invention relates to a resin composition, a cured product, a laminate, a method for manufacturing the cured product, a semiconductor device, and a precursor for a cyclized resin. 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 mounting semiconductor devices, 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 applications, cyclized resins such as polyimide are used in the form of resin compositions comprising precursors of cyclized resins.

[0004] For example, such resin compositions can be applied to a substrate by coating to form a photosensitive film, 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 offering a high degree of design freedom in aspects such as the shape, size, and application location of the resin composition, resulting in excellent manufacturing adaptability. Considering both the high performance of cyclized resins like polyimide and this excellent manufacturing adaptability, the expansion of industrial applications for the aforementioned resin composition is increasingly promising.

[0007] For example, Patent Document 1 describes a photosensitive resin composition having a polymeric precursor and a specific structure that promotes the reaction of the final product by means of an alkaline substance or by heating in the presence of an alkaline substance, and contains an alkali generating agent that generates alkali by means of electromagnetic wave irradiation and heating.

[0008] Patent document 2 describes a resin composition containing the following components (a) to (d).

[0009] (a) Polyimide precursors with specific structural units

[0010] (b) Compounds that generate free radicals by irradiation with active light.

[0011] (c) Compounds with specific structures

[0012] (d) Solvent

[0013] Previous technical documents

[0014] Patent documents

[0015] Patent Document 1: Japanese Patent Application Publication No. 2011-121962

[0016] Patent Document 2: Japanese Patent Application Publication No. 2014-201695 Summary of the Invention

[0017] The technical problem to be solved by the invention

[0018] In a resin composition containing a precursor of a cyclized resin, after a pattern is formed by exposure, development, etc., the precursor of the cyclized resin is cyclized to obtain a pattern of cured material.

[0019] Here, the pattern of the aforementioned cured material is required to have excellent rectangularity.

[0020] Excellent rectangularity of the cured pattern means that the cone angle between the substrate on which the cured product is formed and the side of the cured product does not exceed 90° and the cross-sectional shape of the pattern is not a necked shape, with the cone angle close to 90°.

[0021] Hereinafter, the case of excellent rectangularity of the pattern of the cured material will be referred to simply as "excellent rectangularity of the cured material".

[0022] The present invention aims to provide a resin composition with excellent rectangularity of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a semiconductor device containing the above cured product or the above laminate, a method for manufacturing a cured product that can obtain a cured product with excellent rectangularity, and a precursor of a novel cyclized resin.

[0023] means for solving technical problems

[0024] The following are examples of representative embodiments of the present invention.

[0025] <1> A resin composition comprising a precursor of a cyclized resin.

[0026] The precursor of the cyclized resin mentioned above is a cyclized resin precursor that produces alkali when heated to 250°C.

[0027] <2> according to <1> The resin composition, wherein,

[0028] During the above heating, the alkali is released from the precursor of the cyclized resin.

[0029] <3> according to <1> or <2> The resin composition, wherein,

[0030] The precursor of the aforementioned cyclized resin contains a nonionic structure that exhibits the property of generating alkali.

[0031] <4> according to <1> to <3> The resin composition described in any one of the following statements, wherein,

[0032] The precursors of the aforementioned cyclized resins contain amide bonds, which exhibit the property of generating bases.

[0033] <5> according to <4> The resin composition, wherein,

[0034] The aforementioned amide bond is bonded to the main chain of the precursor of the aforementioned cyclized resin on the carbonyl side.

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

[0036] The precursor of the aforementioned cyclized resin comprises a structure represented by the following formula (1-1).

[0037] [Chemical Formula 1]

[0038]

[0039] In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 They can be connected to form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

[0040] <7> according to <1> to <6> The resin composition described in any one of the following examples further comprises a photopolymerization initiator.

[0041] <8> according to <1> to <7> The resin composition described in any one of the following examples further comprises a polymerizable compound.

[0042] <9> according to <1> to <8> The resin composition described in any one of the following statements further comprises an alkali-generating agent.

[0043] <10> according to <1> to <9> The resin composition described in any one of the following is used to form an interlayer insulating film for a rewiring layer.

[0044] <11> A solidified substance, which is cured <1> to <10> It is made of the resin composition described in any one of the above.

[0045] <12> A laminate comprising two or more layers made of <11> The layers composed of the cured material contain metal layers between any of the layers composed of the cured material.

[0046] <13> A semiconductor device comprising <11> The solidified material or <12> The aforementioned laminated body.

[0047] <14> A method for manufacturing a solidified material, comprising:

[0048] In the film forming process, a film is formed on a substrate by applying a resin composition containing a precursor of a cyclized resin.

[0049] The exposure process involves selectively exposing the film.

[0050] In the developing process, a developing solution is used to develop the film to form a pattern; and

[0051] The heating process involves heating the pattern at a temperature above 50°C and below 250°C.

[0052] The precursor of the cyclized resin is a compound that generates an alkali during the heating process described above.

[0053] <15> according to <14> The method for manufacturing the solidified material, wherein,

[0054] Regarding the film after the exposure process and before the development process, the ratio F / E of the number of moles of alkali-generating groups present in the film as the residual pattern after the development process to the number of moles of alkali-generating groups present in the pattern after the development process exceeds 0.9.

[0055] <16> according to <14> or <15> The method for manufacturing the solidified material, wherein,

[0056] In the membrane formed in the above membrane forming process, the ratio of the concentration X of alkali-generating groups in the upper 50% of the membrane thickness direction to the concentration Y of alkali-generating groups in the lower 50% is 0.90 < X / Y < 1.10.

[0057] <17> according to <14> to <16> The method for manufacturing the cured product as described in any one of the following, wherein,

[0058] The ratio of the closed-loop ratio A on the opposite side of the cured product to the closed-loop ratio B on the side of the cured product in contact with the substrate is 0.90 < A / B < 1.10.

[0059] <18> according to <14> to <17> The method for manufacturing the cured product as described in any one of the following, wherein,

[0060] When a 1:1 line and space pattern with a film thickness of 20 μm and a spacing of 10 μm is formed in the developing process, and the pattern is heated at 230°C for 180 minutes in the heating process, the ratio of the width shrinkage rate C at the upper end of the line pattern to the width shrinkage rate D at the lower end, C / D, is 0.90 < C / D < 1.10.

[0061] <19> A precursor of a cyclized resin, comprising at least one repeating unit selected from repeating units represented by formula (2), repeating units represented by formula (3), and repeating units represented by formula (PAI-2).

[0062] [Chemical Formula 2]

[0063]

[0064] 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 independently represent a hydrogen atom or a monovalent organic group, R 111 R 115 R 113 and R 114 At least one of them contains a structure represented by the following equation (1-1),

[0065] [Chemical Formula 3]

[0066]

[0067] In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can independently represent a hydrogen atom or a monovalent organic group, R 121 R 122 R 123 and R 124 At least one of them contains a structure represented by the following equation (1-1).

[0068] [Chemical Formula 4]

[0069]

[0070] In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 R represents a hydrogen atom or a monovalent organic group. 117 R 111 and R 113 At least one of them contains a structure represented by the following equation (1-1),

[0071] [Chemical Formula 5]

[0072]

[0073] In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 They can be connected to form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

[0074] Invention Effects

[0075] According to the present invention, a resin composition with excellent rectangularity of the obtained cured product is provided, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a semiconductor device containing the above cured product or the above laminate, a method for manufacturing a cured product that can obtain a cured product with excellent rectangularity, and a precursor of a novel cyclized resin are provided. Detailed Implementation

[0076] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0077] In this specification, the numerical range represented by the “~” symbol refers to the range included by taking the values ​​before and after the “~” as the lower limit and upper limit, respectively.

[0078] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of the process can be achieved.

[0079] 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).

[0080] 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.

[0081] 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.

[0082] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0083] 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.

[0084] 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) as the column and connecting guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. Where THF is unsuitable as a dissolution solution due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurements uses a UV ray (ultraviolet) detector with a wavelength of 254 nm.

[0085] 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 substrate layers are stacked 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 actual practice, the "upper" direction in this specification may differ from the vertical direction.

[0086] 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.

[0087] 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.

[0088] In this specification, the preferred combination of methods is a more preferred method.

[0089] (Resin Composition)

[0090] The resin composition of the present invention comprises a precursor of a cyclized resin, wherein the precursor of the cyclized resin is a precursor of a cyclized resin that generates an alkali when heated to 250°C.

[0091] Hereinafter, the precursor of cyclized resin and the resin that produces alkali when heated to 250°C are also referred to as "specific resin".

[0092] Furthermore, the specific resin preferably generates alkali by heating to 220°C, more preferably by heating to 200°C, even more preferably by heating to 190°C, and especially preferably by heating to 180°C. The lower limit of the temperature for generating alkali is not particularly limited, but from the viewpoint of the storage stability of the composition, for example, 100°C or higher is preferred.

[0093] 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.

[0094] 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 is preferably used to form interlayer insulating films for rewiring layers.

[0095] 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.

[0096] In this invention, negative development refers to the development that removes the non-exposed areas during exposure and development, while positive development refers to the development that removes the exposed areas during development.

[0097] 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.

[0098] The cured products obtained by means of the resin composition of the present invention exhibit excellent rectangularity.

[0099] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0100] Previously, by including an alkali-generating agent in the resin composition containing the cyclized resin precursor, the ring-closing rate during heating was increased, and the elongation at break of the obtained cured product was improved.

[0101] Here, the inventors have conducted in-depth research and found that when using conventional alkali generating agents, the alkali generating agents are sometimes not easily distributed uniformly in the film, resulting in poor rectangularity of the obtained cured pattern.

[0102] It is believed that because the molecular weight of the alkali-generating agent is generally smaller than that of the resin, such as the precursor of the cyclizing resin, it can sometimes lead to a large distribution on the surface of the film opposite to the substrate. In this case, cyclization is easier to occur near the surface of the film opposite to the substrate, while it is less likely to occur near the substrate side of the film (i.e., the deeper side of the film). Here, film shrinkage occurs when the precursor of the cyclizing resin cyclizes. Film shrinkage refers to the reduction (shrinkage) in volume of the cured product (e.g., cured film) after curing compared to the composition before curing (e.g., the composition film before heating). For example, as described above, when cyclization is easier to occur near the surface of the film opposite to the substrate and less likely to occur near the substrate, film shrinkage is more likely to occur on the side of the film opposite to the substrate, and the shape of the cured product may sometimes become a conical shape.

[0103] In this invention, a precursor of a cyclized resin (a specific resin) that generates an alkali when heated to 250°C is used as the precursor of the cyclized resin. Therefore, it is believed that in this invention, the structure exhibiting the property of generating an alkali is distributed in a nearly uniform manner throughout the film, thus reducing the likelihood of differences in film shrinkage due to location, thereby improving the rectangularity of the pattern.

[0104] Furthermore, it is speculated that by using the aforementioned specific resin, the dissolution of alkali-generating agents caused by development can be suppressed during development, thus resulting in a relatively large amount of alkali generated during subsequent heating, and an increased elongation at break of the obtained cured product.

[0105] Furthermore, when an alkali-generating agent with a molecular weight lower than that of the resin locally aggregates in the film, the solubility of the developer around the aggregate differs from that of the unaggregated areas (e.g., resin-rich areas such as cyclized resin precursors). Therefore, the roughness of the pattern (e.g., line edge roughness, line width roughness) may sometimes increase when patterns are formed by development.

[0106] According to the present invention, it is speculated that the structure exhibiting the property of generating alkali is distributed in a nearly uniform manner throughout the membrane, thereby reducing the aforementioned roughness.

[0107] Here, patent documents 1 and 2 do not describe the use of a specific resin.

[0108] The components contained in the resin composition of the present invention will be described in detail below.

[0109] <Specific Resin>

[0110] The resin composition of the present invention comprises a precursor of a cyclized resin, wherein the precursor of the cyclized resin is a precursor of a cyclized resin that generates an alkali when heated to 250°C.

[0111] Cyclic resins are preferably resins that contain an imide ring structure or an oxazole ring structure in their main chain structure.

[0112] In this invention, the main chain refers to the longest bonded chain in the resin molecule.

[0113] Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide.

[0114] The precursor of a cyclized resin refers to a resin whose chemical structure changes due to external stimuli to become a cyclized resin. Preferably, it is a resin whose chemical structure changes due to heat to become a cyclized resin, and more preferably, it is a resin that becomes a cyclized resin by forming a ring structure through a ring-closing reaction caused by heat.

[0115] Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0116] That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from polyimide precursor, polybenzoxazole precursor and polyamide-imide precursor as a specific resin.

[0117] The resin composition of the present invention preferably contains a polyimide precursor as a specific resin.

[0118] [The production of alkali]

[0119] Some resins produce alkali when heated to 250°C.

[0120] One mole of resin is placed in a sealed container. The container is heated at 250°C for 3 hours under 1 atmosphere pressure. The amount of alkali produced is then quantified using HPLC (High-Speed ​​Liquid Chromatography). The production of 0.01 moles or more of alkali is considered "alkali production." The 1 mole of resin, whether liquid or solid, is placed in the sealed container with a thickness of 0.50 cm or less. The production amount is preferably 0.1 moles or more, more preferably 1 mole or more. There is no particular upper limit to the production amount; for example, it can be set to 1000 moles or less.

[0121] From the viewpoint of the elongation at break of the obtained cured product, the alkali generated from a particular resin is preferably an amine, more preferably a secondary amine or a tertiary amine, and even more preferably a secondary amine.

[0122] Furthermore, when an amine is generated from a specific resin, the amine can be an aliphatic amine or an aromatic amine, but from the viewpoint of suppressing the shrinkage of the cured product, an amine having an aromatic ring structure is preferred. There is no particular limitation on the aforementioned aromatic ring structure, but an aromatic hydrocarbon ring structure is preferred, and a benzene ring structure is more preferred.

[0123] The resulting base is preferably a base with a pKa of 0 or higher for the conjugate acid, more preferably a base with a pKa of 3 or higher, and even more preferably a base with a pKa of 6 or higher. There is no particular upper limit to the pKa of the conjugate acid, but it is preferably 30 or lower.

[0124] pKa is the equilibrium constant Ka, which takes into account the dissociation reaction of an acid releasing hydrogen ions, and is expressed by its negative common logarithm, pKa. In this specification, unless otherwise specified, pKa is assumed to be a value calculated based on ACD / Chem Sketch (registered trademark).

[0125] When multiple pKas of the aforementioned conjugate acids exist, it is preferable that at least one is within the aforementioned range.

[0126] From the viewpoint of elongation at break, it is preferable that the alkali generated from the specific resin is released from the precursor of the cyclized resin during the above-mentioned heating.

[0127] The aforementioned alkali can be released from the precursor of the cyclized resin by cracking at the alkali generation site during heating, or it can be released from the precursor of the cyclized resin as the cyclized resin closure occurs.

[0128] When the above-mentioned alkali is released from the precursor of the cyclized resin, the molecular weight of the resulting alkali is preferably 70 to 500, more preferably 80 to 300, and even more preferably 90 to 220.

[0129] Furthermore, when the alkali is released from the precursor of the cyclized resin, the boiling point of the alkali produced at 1 atmosphere is preferably 50 to 450°C, more preferably 60 to 400°C, and even more preferably 80 to 350°C.

[0130] Furthermore, the resins that retain alkali in a particular resin when heated can also be used as the specific resins of the present invention.

[0131] Specific examples of the bases produced include, but are not limited to, the bases described below. These bases may exist in their free state as bases, or they may exist as structures formed by removing some of the hydrogen atoms from these bases and bonding them to a specific resin after the base is produced.

[0132] [Chemical Formula 6]

[0133]

[0134] [Structures that demonstrate the property of producing bases]

[0135] A particular resin preferably contains a structure that exhibits the property of generating alkali.

[0136] The structure exhibiting the property of producing alkali can be either an ionic structure or a nonionic structure. From the viewpoint of the rectangularity of the obtained cured product, a nonionic structure is preferred.

[0137] As an ionic structure, the quaternary ammonium cation structure can be cited as an example.

[0138] As nonionic structures, examples include structures containing amide bonds or carbamate bonds.

[0139] In a particular resin, 1 to 1000 moles of a structure exhibiting alkali-generating properties are preferably included relative to 1 mole of the particular resin, more preferably 2 to 800 moles, and even more preferably 5 to 500 moles.

[0140] Of these, from the viewpoint of the rectangularity of the obtained cured product, the structure that exhibits the property of producing alkali preferably contains amide bonds.

[0141] In addition to the so-called amide bonds represented by (*-C(=O)NH-#), the amide bonds in certain resins also include the so-called substituted amide bonds represented by (*-C(=O)NR-#). The * and # above represent bonding sites with other structures, respectively. It is particularly preferred that both * and # are bonding sites with carbon atoms.

[0142] The substituent (R above) in the amide bond is not particularly limited, and known substituents can be used, such as alkyl, aromatic hydrocarbon groups, or combinations thereof. These hydrocarbon groups can be further substituted with halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, hydroxyl groups, etc.

[0143] Furthermore, the aforementioned hydrocarbon group can bond with at least one of the nitrogen atoms in the aforementioned substituted amide bond and the structure bonded to the # site to form a ring structure. Examples of the formed ring structures include piperidine rings and morpholine rings, where the nitrogen atom contained in the aforementioned amide bond is a ring element. These ring structures may further have substituents. Examples of substituents include groups identical to the substituents in the aforementioned hydrocarbon group.

[0144] Among these, from the viewpoint that the resulting alkali is highly basic and easily increases the elongation at break, the amide bond in a particular resin is preferably a substituted amide bond, and more preferably a substituted amide bond having a hydrocarbon group as a substituent.

[0145] The amide bond is preferably bonded to the main chain of the cyclized resin precursor on the carbonyl side. Thus, the resulting base can be released from the specific resin by breaking the amide bond.

[0146] The carbonyl side of the amide bond in a specific resin refers to the * side in (*-C(=O)NH-#) or (*-C(=O)NR-#) mentioned above.

[0147] [The structure represented by equation (1-1)]

[0148] The particular resin preferably contains a structure represented by the following formula (1-1). Moreover, it is preferable that the amide group in formula (1-1) cracks to produce an alkali during the above-mentioned heating.

[0149] [Chemical Formula 7]

[0150]

[0151] In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 They can be connected to form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

[0152] -R 1 -

[0153] From the perspective of elongation at break, in equation (1-1), R 1 Preferably, each is an independent monovalent organic group.

[0154] R 1 Preferably, it is a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group, or a combination thereof, and even more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof, especially preferably an alkyl group having 1 to 10 carbon atoms.

[0155] The alkyl group can be any of the following: linear, branched, or cyclic. From the viewpoint of improving elongation at break, branched alkyl groups (e.g., isopropyl, isobutyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (e.g., cyclohexyl, etc.) are preferred.

[0156] R 1 It can have substituents, and examples of substituents include halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, and hydroxyl groups.

[0157] As 2 R 1The resulting ring structures include, for example, piperidine rings and morpholine rings, in which the nitrogen atom contained in the amide bond is a ring element. These ring structures may further have substituents. Examples of substituents include groups identical to the substituents in the aforementioned hydrocarbon groups.

[0158] As R 1 Examples of preferred embodiments include the following structures. The nitrogen atom in the structures of the following specific examples refers to the nitrogen atom contained in the amide bond of formula (1-1). In the following specific examples, * indicates the bonding site with the carbonyl group.

[0159] [Chemical Formula 8]

[0160]

[0161] -L 1 -

[0162] In equation (1-1), L 1 There are no particular limitations, but it is preferred to have a hydrocarbon group or a combination of one or more hydrocarbon groups and a group selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR. N - A group represented by at least one type of bond in the structure 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.

[0163] As the aforementioned hydrocarbon group, saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by bonds of these are preferred.

[0164] As the aforementioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms is more preferred.

[0165] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms, preferably those formed by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably those formed by removing multiple hydrogen atoms from a benzene ring.

[0166] Aliphatic hydrocarbon cyclic groups can be used as the aforementioned aliphatic hydrocarbon groups. There are no particular limitations on the aliphatic hydrocarbon cyclic group; examples include groups formed by removing multiple hydrogen atoms from a dicyclopentane ring, a borneol ring, an isoborneol ring, or an adamantane ring.

[0167] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms, preferably those formed by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably those formed by removing multiple hydrogen atoms from a benzene ring.

[0168] Furthermore, the aforementioned aromatic hydrocarbon groups or aliphatic hydrocarbon cyclic groups can condense with other rings. Examples of this type include groups formed by removing multiple hydrogen atoms from a phthalimide ring.

[0169] From the perspective of the elongation at break and chemical resistance of the obtained cured product, L, as the aforementioned hydrocarbon group, 1 Preferably, it contains an aromatic hydrocarbon group, and more preferably, it contains a group formed by removing multiple hydrogen atoms from a benzene ring.

[0170] Furthermore, from the perspective of alkali production efficiency, L is preferred. 1 When it contains aromatic hydrocarbon groups, L 1 The aromatic hydrocarbon groups in L are directly bonded to the hydroxyl groups in formula (1-1). 1 When the aromatic hydrocarbon group in formula (1-1) is directly bonded to the hydroxyl group in formula (1-1), the above hydroxyl group and L 1 The site where the aromatic hydrocarbon group is directly or via a linker group to the amide bond is preferably located in L. 1 The ortho position refers to the position of an aromatic hydrocarbon group in a benzene ring. An ortho position means that the ring member bonded to one substituent in an aromatic hydrocarbon group is adjacent to the ring member bonded to another substituent.

[0171] Furthermore, the OH group in formula (1-1) can be part of a carboxyl group. In this case, L is preferred. 1 The aromatic hydrocarbon groups in L are directly bonded to the aforementioned carboxyl groups. Furthermore, L 1 When the aromatic hydrocarbon group in the above-mentioned carboxyl group is directly bonded, the above-mentioned hydroxyl group and L 1 The site where the aromatic hydrocarbon group is directly or via a linker group to the amide bond is preferably located in L. 1 The ortho position of the aromatic hydrocarbon group in the group.

[0172] As L 1 Examples of preferred embodiments include the following structures. In the following specific examples, # represents the bonding site with the carbonyl group in formula (1-1), and * has the same meaning as * in formula (1-1). Moreover, the OH in the following specific examples is the OH in formula (1-1).

[0173] [Chemical Formula 9]

[0174]

[0175] [The structure represented by equation (1-2)]

[0176] The specific resin also preferably contains a structure represented by the following formula (1-2) as a structure that exhibits the property of producing an alkali.

[0177] [Chemical Formula 10]

[0178]

[0179] In equation (1-2), R 1 Each of the two Rs can independently represent a hydrogen atom or a monovalent organic group. 1 They can be connected to form a ring structure, L 2 The symbol indicates a single bond or a divalent linker; Cy indicates a ring structure; and * indicates a bonding site with other structures.

[0180] -R 1 -

[0181] In equation (1-2), R 1 R in equation (1-1) 1 The meanings are the same, and the preferred selection methods are also the same.

[0182] -L 2 -

[0183] In equation (1-2), L 2 This indicates a single bond or a divalent linkage, preferably a single bond or a hydrocarbon group, or a combination of one or more hydrocarbon groups and a linkage selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR. N A group represented by a bond of at least one structure selected from -O- and -C(=O)-, more preferably a single bond or a hydrocarbon group, or a group represented by a bond of one or more hydrocarbon groups and at least one structure selected from -O- and -C(=O)-. N As described above.

[0184] As the aforementioned hydrocarbon group, alkylene groups, divalent aromatic hydrocarbon groups, or groups represented by bonds of these are preferred.

[0185] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, and alkylene groups having 1 to 10 carbon atoms are more preferred.

[0186] Examples of divalent aromatic hydrocarbon groups include aromatic hydrocarbon groups with 6 to 20 carbon atoms, with phenylene or naphthylene being preferred, and phenylene being more preferred.

[0187] -Cy-

[0188] In equation (1-2), Cy represents a ring structure.

[0189] As a ring structure, it can be either an aliphatic ring structure or an aromatic ring structure, with an aromatic ring structure being preferred.

[0190] Furthermore, it can be either a hydrocarbon ring structure or a heterocyclic structure, with a hydrocarbon ring structure being preferred. Examples of heteroatoms included in the aforementioned heterocyclic structure include oxygen atoms, sulfur atoms, and nitrogen atoms. Moreover, examples of the aforementioned heterocyclic structure include aromatic heterocyclic structures, with pyrrole, indole, furan, benzofuran, thiophene, and benzothiophene being preferred.

[0191] From the perspective of alkali production efficiency, Cy is preferably an aliphatic hydrocarbon ring structure or an aromatic hydrocarbon ring structure.

[0192] Examples of aliphatic hydrocarbon ring structures include bicyclopentane rings, borneol rings, isoborneol rings, and adamantane rings, with bicyclopentane rings being preferred.

[0193] As for the above-mentioned aromatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure with 6 to 20 carbon atoms is preferred, a benzene ring structure or a naphthalene ring structure is more preferred, and a benzene ring structure is even more preferred.

[0194] Furthermore, the aforementioned aromatic hydrocarbon ring structures or aliphatic hydrocarbon ring structures can condense with other rings. Examples of this type include phthalimide ring structures.

[0195] From the perspective of alkali production efficiency, Cy is preferably a dicyclopentane ring structure or a benzene ring structure, and more preferably a benzene ring structure.

[0196] Furthermore, Cy can have substituents.

[0197] When Cy is an aromatic ring (preferably an aromatic hydrocarbon ring), from the viewpoint of base production efficiency, the preferred bonding position of Cy with the hydroxyl group in formula (1-2) is the L-position of Cy. 2 The neighboring position.

[0198] For example, when Cy is a benzene ring, it is preferred to have L 2 The adjacent position has a hydroxyl group as shown in formula (1-2).

[0199] Furthermore, the OH group in formula (1-2) can be part of a carboxyl group. When the aromatic hydrocarbon group in Cy is directly bonded to the aforementioned carboxyl group, the preferred bonding position of Cy with the aforementioned carboxyl group is the L group in Cy. 2 The neighboring position.

[0200] [The structure represented by equation (1-3)]

[0201] The specific resin also preferably contains a structure represented by the following formulas (1-3) as a structure that exhibits the property of producing alkali.

[0202] [Chemical Formula 11]

[0203]

[0204] In equation (1-3), R 1 R is a hydrogen atom or a monovalent organic group. 3 It is a divalent organic group, L 3 R is a divalent organic group. 1 With L 3They can be linked to form a ring structure, and * indicates the bonding site with other structures.

[0205] -R 1 -

[0206] In equation (1-3), R 1 R in equation (1-1) above 1 The meanings are the same, and the preferred selection methods are also the same.

[0207] -R 3 -

[0208] In equation (1-3), R 3 There are no particular limitations, but a hydrocarbon group or a combination of one or more hydrocarbon groups and a group selected from -O-, -S-, -C(=O)-, -S(=O)2- and -NR is preferred. N - A group represented by at least one type of bond in the structure R. N As described above.

[0209] As the aforementioned hydrocarbon group, saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by bonds of these are preferred.

[0210] As the aforementioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms is more preferred.

[0211] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms, preferably those formed by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably those formed by removing multiple hydrogen atoms from a benzene ring.

[0212] Aliphatic hydrocarbon cyclic groups can be used as the aforementioned aliphatic hydrocarbon groups. There are no particular limitations on the aliphatic hydrocarbon cyclic group; examples include groups formed by removing multiple hydrogen atoms from a dicyclopentane ring, a borneol ring, an isoborneol ring, or an adamantane ring.

[0213] Examples of aromatic hydrocarbon groups include those with 6 to 20 carbon atoms, preferably those formed by removing multiple hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably those formed by removing multiple hydrogen atoms from a benzene ring.

[0214] Furthermore, the aforementioned aromatic hydrocarbon groups or aliphatic hydrocarbon cyclic groups can condense with other rings. Examples of this type include groups formed by removing multiple hydrogen atoms from a phthalimide ring.

[0215] From the perspective of the elongation at break and chemical resistance of the obtained cured product, R, as the aforementioned hydrocarbon group, 3 Preferably, it contains an aromatic hydrocarbon group, and more preferably, it contains a group formed by removing multiple hydrogen atoms from a benzene ring.

[0216] Furthermore, from the perspective of alkali production efficiency, R is preferred. 3 When it contains aromatic hydrocarbon groups, R 3 The aromatic hydrocarbon group in R is directly bonded to the hydroxyl group in formula (1-3). 3 When the aromatic hydrocarbon group in formula (1-3) is directly bonded to the hydroxyl group in formula (1-3), the above hydroxyl group and R 3 The site where the aromatic hydrocarbon group is directly or via a linker group to the amide bond is preferably located in R. 3 The ortho position refers to the position of an aromatic hydrocarbon group in a benzene ring. An ortho position means that the ring member bonded to one substituent in an aromatic hydrocarbon group is adjacent to the ring member bonded to another substituent.

[0217] Furthermore, the OH group in formula (1-3) can be part of a carboxyl group. In this case, R is preferred. 3 The aromatic hydrocarbon groups in R are directly bonded to the aforementioned carboxyl groups. Furthermore, R 3 When the aromatic hydrocarbon group in the above-mentioned carboxyl group is directly bonded, the above-mentioned hydroxyl group and R 3 The site where the aromatic hydrocarbon group is directly or via a linker group to the amide bond is preferably located in R. 3 The ortho position of the aromatic hydrocarbon group in the group.

[0218] -L 3 -

[0219] In equation (1-3), L 3 There are no particular limitations, but a hydrocarbon group is preferred, more preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these, and even more preferably a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms, or a group represented by a combination of these, and especially preferably a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms.

[0220] L 3 It can have substituents, and examples of substituents include halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, and hydroxyl groups.

[0221] As R 1 With L 3 The resulting ring structures include, for example, piperidine rings and morpholine rings, in which the nitrogen atom contained in the amide bond is a ring element. These ring structures may further have substituents. Examples of substituents include groups identical to the substituents in the aforementioned hydrocarbon groups.

[0222] Furthermore, as structures that exhibit the property of producing alkali, examples can be given by the structures represented by the following formulas (1-4) to (1-5).

[0223] [Chemical Formula 12]

[0224]

[0225] In equation (1-4), R 1 R represents a hydrogen atom or a monovalent organic group. 4 Each can independently represent a hydrogen atom or a monovalent organic group; R is not present. 4 In the case where all atoms are hydrogen atoms, R 1 and R 4 Each of them contains bonding sites with other structures.

[0226] In equation (1-4), R 1 When it does not contain bonding sites with other structures, R 1 R in equation (1-1) 1 The meanings are the same, and the preferred selection methods are also the same.

[0227] In equation (1-4), R 1 When it includes bonding sites with other structures, R 1 L in equation (1-3) 3 The meaning of bonding site (*) is the same, and the preferred method is also the same.

[0228] In equation (1-4), R 4 When it does not contain bonding sites with other structures, R 4 Examples of preferred components include hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, 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), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and more preferably hydrogen atoms or methyl groups.

[0229] In equation (1-4), R 4 When it includes bonding sites with other structures, R 4 Examples of preferred groups include alkylene groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, 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) or groups represented by bonds thereof, with alkylene groups being more preferred.

[0230] In equation (1-5), R 5 Each independently represents a monovalent organic group, R 5 Each of them contains a bonding site with other structures, and A represents a counter anion with a valence of 1 or higher.

[0231] In equation (1-5), R is preferred. 5 The hydrocarbon group is not included in the bonding sites with other structures and is represented independently. Examples of hydrocarbon groups include alkyl (preferably 1-12 carbon atoms, more preferably 1-6, and even more preferably 1-3), alkenyl (preferably 2-12 carbon atoms, more preferably 2-6, and even more preferably 2-3), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), arylalkyl (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-11), alkyl is more preferred, and methyl is even more preferred.

[0232] In equation (1-5), R 5 The portion containing the bonding portion with other structures is similar to L in equation (1-3). 3 The meaning of bonding site (*) is the same, and the preferred method is also the same.

[0233] In formulas (1-5), A represents the counter anion. A is preferably an anion with a pKa1 of 0 to 4. Moreover, A is preferably a carboxylic acid anion, phenolic anion, phosphate anion, or sulfate anion, and carboxylic acid anion is more preferred from the perspective of balancing salt stability and thermal decomposition.

[0234] The aforementioned carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid.

[0235] The aforementioned carboxylic acid anion is preferably an anion of carboxylic acid with a pKa1 of 4 or less. More preferably, the pKa1 is 3.5 or less, and even more preferably 3.2 or less. According to this method, the stability of the resin composition can be further improved.

[0236] Where pKa1 represents the logarithm of the inverse of the first dissociation constant of the acid, and can be referenced to the values ​​described in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; eds.: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, RMC et al.; Oxford, Clarendon Press, 1959). For compounds not described in these publications, values ​​calculated from the structural formula using ACD / pKa (ACD / Labs software) are used.

[0237] Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0238] 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. Such resin compositions of the present invention can be used to form, for example, negative photosensitive films.

[0239] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0240] 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.

[0241] [Polyimide precursor]

[0242] 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).

[0243] [Chemical Formula 13]

[0244]

[0245] In equation (2), A 1 and A 2 Each independently represents 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.

[0246] When a particular resin contains a repeating unit represented by formula (2), the particular resin preferably contains a structure exhibiting the property of generating an alkali within the repeating unit represented by formula (2), and more preferably contains a structure represented by formula (1-1) above within the repeating unit represented by formula (2).

[0247] For example, R is preferably selected from formula (2). 111 R 113 R 114 and R 115 At least one of the structures contains the structure exhibiting the above-described properties of producing an alkali (preferably the structure represented by formula (1-1)), more preferably R selected from formula (2). 113 and R 114 At least one of the structures contains the structure that exhibits the property of producing an alkali (preferably the structure represented by formula (1-1)).

[0248] Furthermore, when a particular resin contains a repeating unit represented by formula (2), the particular resin may contain a structure exhibiting alkali-generating properties at a location different from the repeating unit represented by formula (2). For example, examples include a particular resin containing a structure exhibiting alkali-generating properties at the end, or a particular resin further containing a repeating unit different from the repeating unit represented by formula (2) and containing a structure exhibiting alkali-generating properties.

[0249] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, with oxygen atom being preferred.

[0250] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and 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 comprising aromatic groups with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the hydrocarbon group of the cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. As a preferred embodiment of the invention, groups represented by -Ar- and -Ar-L-Ar- are examples, with groups represented by -Ar-L-Ar- being particularly preferred. In this group, Ar is an aromatic group, and 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.

[0251] 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.

[0252] Specifically, diamines preferably contain a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof; more preferably, diamines contain an aromatic group with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group of the cyclic aliphatic group and the aromatic group can be replaced by a group containing a heteroatom. Examples of groups containing aromatic groups include the following groups.

[0253] [Chemical Formula 14]

[0254]

[0255] In the formula, A represents a single bond or a divalent group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted 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 substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0256] In the formula, * indicates the bonding site with other structures.

[0257] As a diamine, examples specifically include those selected from 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)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-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, diaminotriphenylamine Fluorotoluene, 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-(4-aminophenoxy)-3,5-fluoropropane [-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)diphenyl sulfone, 4 At least one diamine selected from the following: 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'-hexafluorobitoluene, and 4,4'-diaminotetraphenyl.

[0258] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0259] 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.

[0260] From the viewpoint of the flexibility of the obtained organic membrane, R is preferred. 111 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 consisting 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.

[0261] Furthermore, from the viewpoint of i-ray transmittance, R is preferred. 111 It is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable to be a divalent organic group represented by formula (61).

[0262] Equation (51)

[0263] [Chemical Formula 15]

[0264]

[0265] 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.

[0266] 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).

[0267] [Chemical Formula 16]

[0268]

[0269] 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).

[0270] 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.

[0271] 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.

[0272] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0273] [Chemical Formula 17]

[0274]

[0275] 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-.

[0276] Moreover, R 111 It can also contain structures that exhibit the property of producing alkali.

[0277] R 111 When it contains a structure that exhibits the property of producing a base, for example, R 111 The preferred structure is represented by the following formula (LD-1).

[0278] [Chemical Formula 18]

[0279]

[0280] In equation (LD-1), Y D1 P represents an n+2 valence organic group. D1 The symbol represents a group containing a structure that exhibits the property of producing a base, n represents an integer greater than 1, and * represents R in equation (2). 111 The bonding sites of the nitrogen atoms.

[0281] -Y D1 -

[0282] In equation (LD-1), Y D1 Preferably, it is an n+2 valent organic group, more preferably an n+2 valent organic group containing an aromatic hydrocarbon group.

[0283] Y D1 The aromatic hydrocarbon group in the form is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, even more preferably a group formed by removing 2 or more hydrogen atoms from the benzene ring, and especially preferably a group formed by removing 3 or more hydrogen atoms from the benzene ring.

[0284] In equation (LD-1), Y D1The sites in which the two bonding sites (*) described in formula (LD-1) are directly bonded are preferably aromatic hydrocarbon groups. That is, preferably, the two * sites described in formula (LD-1) are directly bonded to Y. D1 The aromatic hydrocarbon ring structures contained therein are directly bonded.

[0285] Moreover, in equation (LD-1), Y D1 In P D1 The bonding sites are preferably all aromatic hydrocarbon groups. That is, P is preferred. D1 With Y D1 The aromatic hydrocarbon ring structures contained therein are directly bonded.

[0286] Y D1 Preferably, it includes at least one structure selected from the structures represented by equations (A2-1) to (A2-5) below, Y D1 More preferably, at least one structure is selected from the structures represented by the above formulas (A2-1) to (A2-5).

[0287] [Chemical Formula 19]

[0288]

[0289] In equations (A2-1) to (A2-5), R A211 ~R A214 R A221 ~R A224 R A231 ~R A238 R A241 ~R A248 and R A251 ~R A258 Each of the following can be independently represented: hydrogen atom, alkyl group, cyclic alkyl group, alkoxy group, hydroxyl group, cyano group, haloalkyl group, or halogen atom. A231 and L A241 Each of these groups independently represents a single bond, carbonyl group, sulfonyl group, divalent saturated hydrocarbon group, divalent unsaturated hydrocarbon group, heteroatom, heterocyclic group, or alkyl halide, R. A211 ~R A214 At least one of them, R A221 ~R A224 At least one of them, R A231 ~R A238 At least one of them, R A241 ~R A248 At least one of them and R A251 ~R A258 At least one of them can be the structure that exhibits the property of producing a base, and * represents the bonding site with other structures independently.

[0290] Of these, from the perspective of solvent solubility, Y1 Preferably, it includes a structure represented by any one of formulas (A2-1) to (A2-4), and more preferably, it includes a structure represented by any one of formulas (A2-1) or (A2-4).

[0291] R A211 ~R A214 At least one of them, R A221 ~R A224 At least one of them, R A231 ~R A238 At least one of them, R A241 ~R A248 At least one of them and R A251 ~R A258 At least one of them is preferably P in the above formula (LD-1). D1 The bonding sites.

[0292] In equation (A2-1), R A211 ~R A214 Not with P D1 When bonding to the site, R A211 ~R A214 Preferably, each of the following is independently represented: hydrogen atom, alkyl group with 1 to 6 carbon atoms, cyclic alkyl group with 3 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, hydroxyl group, cyano group, halogenated alkyl group with 1 to 3 carbon atoms, or halogen atom. From the viewpoint of solvent solubility, hydrogen atom, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, halogenated alkyl group with 1 to 3 carbon atoms, and hydrogen atom or alkyl group with 1 to 6 carbon atoms are preferred.

[0293] As mentioned above, R A211 ~R A214 The halogen atom in the aforementioned halogenated alkyl group can be a fluorine atom, chlorine atom, bromine atom, iodine atom, etc., with chlorine atom or bromine atom being preferred.

[0294] R in equation (A2-2) A221 ~R A224 R in equation (A2-1) A211 ~R A214 The meanings are the same, and the preferred methods are also the same.

[0295] In equation (A2-3), R A231 ~R A238Preferably, each of the following is independently represented: hydrogen atom, alkyl group with 1 to 6 carbon atoms, cyclic alkyl group with 3 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, hydroxyl group, cyano group, halogenated alkyl group with 1 to 3 carbon atoms, or halogen atom. From the viewpoint of solvent solubility, hydrogen atom, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, or halogenated alkyl group with 1 to 3 carbon atoms are more preferred, and hydrogen atom or alkyl group with 1 to 6 carbon atoms are even more preferred.

[0296] As mentioned above, R A231 ~R A238 The halogen atom in the aforementioned halogenated alkyl group can be a fluorine atom, chlorine atom, bromine atom, iodine atom, etc., with chlorine atom or bromine atom being preferred.

[0297] In formula (A2-3), L A231 Preferred groups include single bonds, divalent saturated hydrocarbon groups with 1 to 6 carbon atoms, divalent unsaturated hydrocarbon groups with 5 to 24 carbon atoms, -O-, -S-, and -NR. N The R group is a heterocyclic group or a haloalkylene group having 1 to 6 carbon atoms, more preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and even more preferably a single bond or -O-. N As described above.

[0298] The aforementioned divalent unsaturated hydrocarbon group can be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, preferably a divalent aromatic hydrocarbon group.

[0299] As the aforementioned heterocyclic group, it is preferred, for example, to be a group formed by removing two hydrogen atoms from an aliphatic or aromatic heterocycle, more preferably a group formed by removing two hydrogen atoms from aliphatic or aromatic heterocycles, and even more preferably a group formed by removing two hydrogen atoms from the ring structure of a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, morpholine ring, etc. These heterocycles can further form fused rings with other heterocycles or hydrocarbon rings.

[0300] The number of ring elements in the above-mentioned heterocyclic ring is preferably 5 to 10, more preferably 5 or 6.

[0301] Furthermore, oxygen, nitrogen, or sulfur atoms are preferred as heteroatoms in the aforementioned heterocyclic groups.

[0302] Examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms or bromine atoms being preferred.

[0303] R in equation (A2-4) A241 ~R A248 L A241 R in equation (A2-3) A231 ~R A238 LA231 The meanings are the same, and the preferred methods are also the same.

[0304] R in equation (A2-5) A251 ~R A258 R in equation (A2-1) A211 ~R A214 The meanings are the same, and the preferred methods are also the same.

[0305] In formula (A2-1), R is preferred. A211 ~R A214 At least one of them is P in equation (LD-1) D1 The bonding site, preferably R A211 ~R A214 One of them is related to the above P. D1 The bonding site, preferably R A213 To be consistent with the above P D1 The bonding sites.

[0306] In formula (A2-2), R is preferred. A221 ~R A224 At least one of them is P in equation (LD-1) D1 The bonding site, preferably R A221 ~R A224 One of them is related to the above P. D1 The bonding site is preferably R. A223 To be consistent with the above P D1 The bonding sites.

[0307] In formula (A2-3), R is preferred. A231 ~R A238 At least one of them is P in equation (LD-1) D1 The bonding site, preferably R A231 ~R A238 Two of them are related to P mentioned above. D1 The bonding sites are further optimized for R. A231 ~R A234 1 in and R A235 ~R A238 One of them, totaling two, is related to the above P. D1 The bonding sites, especially R, are preferred. A231 and R A238 These two are related to the above P. D1 The bonding sites.

[0308] In formula (A2-4), R is preferred. A241 ~R A248 At least one of them is P in equation (LD-1) D1 The bonding site, preferably R A241 ~RA248 Two of them are related to P mentioned above. D1 The bonding sites are further optimized for R. A241 ~R A244 1 in and R A245 ~R A248 One of them, totaling two, is related to the above P. D1 The bonding sites, especially R, are preferred. A241 and R A248 These two are related to the above P. D1 The bonding sites.

[0309] In formula (A2-5), R is preferred. A251 ~R A258 At least one of them is P in equation (LD-1) D1 The bonding site, preferably R A251 ~R A258 Two of them are related to P mentioned above. D1 The bonding sites are further optimized for R. A251 ~R A254 1 in and R A255 ~R A258 One of them, totaling two, is related to the above P. D1 The bonding sites, especially R, are preferred. A253 and R A257 These two are related to the above P. D1 The bonding sites.

[0310] In equations (A2-1) to (A2-5), the two asterisks are preferably the asterisks in equation (LD-1). That is, R in equation (2) 111 The two nitrogen atoms bonded are preferably directly bonded to the two positions indicated by * in formulas (A2-1) to (A2-5).

[0311] Among these, Y D1 Preferably, it is a group represented by the following formula (Y-1) or (Y-2).

[0312] [Chemical Formula 20]

[0313]

[0314] R in equation (Y-1) Y11 R Y12 R Y13 respectively with R in equation (A2-1) A211 R A212 and R A214 The meanings are the same, and the preferred selection methods are also the same.

[0315] R in equation (Y-2) Y21 ~R Y26 LX21 respectively with R in equation (A2-4) A242 ~R A247 L A241 The meanings are the same, and the preferred selection methods are also the same.

[0316] In equation (Y-1) or equation (Y-2), * represents R in equation (2), respectively. 111 The bonding sites of the two nitrogen atoms are shown, with # representing the bonding sites with P in formula (LD-1). D1 The bonding sites.

[0317] -P D1 -

[0318] In equation (LD-1), P D1 This indicates a group that contains the structure described above, which exhibits the property of producing a base.

[0319] For example, P D1 The preferred formula is (PD-1).

[0320] [Chemical Formula 21]

[0321] *-L P -R P (PD-1)

[0322] In formula (PD-1), R P The above structures demonstrate the property of producing a base; * indicates the relationship with Y. D1 The bonding site, L P This indicates a divalent linked base.

[0323] As L P Examples include -OC(=O)-, -C(=O)O-, and -C(=O)NR. N -、-OC(=O)NR N -、-NR N C(=O)O-、-NR N C(=O)NR N -etc., preferably -O- or -C(=O)O-. The above R N As described above.

[0324] The preferred manner of the structure that exhibits the property of producing an alkali is as described above. For example, the structure represented by formula (1-1), the structure represented by formula (1-2), etc., can be preferred.

[0325] -n-

[0326] In formula (LD-1), n ​​represents an integer greater than or equal to 1, preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0327] -Synthesis Method-

[0328] For example, the structure represented by the above formula (LD-1) can be obtained as a structure derived from the diamine represented by the following formula (LDA-1).

[0329] [Chemical Formula 22]

[0330]

[0331] In the above formula (LDA-1), Y D1 P D1 , n and Y in the above formula (LD-1) are respectively D1 P D1 The meanings of 'n' and 'n' are the same, and their optimization methods are also the same.

[0332] Furthermore, for example, a specific resin can be synthesized by using a diamine having reactive groups such as carboxyl groups to synthesize a resin, and by reacting a compound having a structure that reacts with the aforementioned reactive groups to form covalent bonds (e.g., hydroxyl groups) and exhibiting the property of producing a base with the aforementioned resin, thereby synthesizing a specific resin.

[0333] 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.

[0334] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0335] [Chemical Formula 23]

[0336]

[0337] 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.

[0338] 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.

[0339] 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.

[0340] In equation (2), it can also be R. 111 and R 115 At least one of them has an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0341] Moreover, R 115 It can also contain structures that exhibit the property of producing alkali.

[0342] R 115 When it contains a structure that exhibits the property of producing a base, for example, R 115 The preferred structure is represented by the following formula (LD-2).

[0343] [Chemical Formula 24]

[0344]

[0345] In equation (LD-2), Y D2 P represents an n+4 valence organic group.D2 The group represents a structure that exhibits the property of producing a base, m represents an integer greater than 1, and * represents R in equation (2). 115 The bonding sites of the carbonyl groups.

[0346] -Y D2 -

[0347] In equation (LD-2), Y D2 Preferably, it is an n+4 valent organic group, more preferably an n+4 valent organic group containing an aromatic hydrocarbon group.

[0348] Y D4 The aromatic hydrocarbon group in the form is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, even more preferably a group formed by removing 2 or more hydrogen atoms from the benzene ring, and especially preferably a group formed by removing 3 or more hydrogen atoms from the benzene ring.

[0349] In equation (LD-2), Y D2 The sites in which the * is directly bonded to the bonding sites described in formula (LD-2) are preferably aromatic hydrocarbon groups. That is, preferably the four * groups described in formula (LD-2) are bonded to Y. D2 The aromatic hydrocarbon ring structures contained therein are directly bonded.

[0350] Moreover, in equation (LD-2), P D2 In P D2 The bonding sites are preferably all aromatic hydrocarbon groups. That is, P is preferred. D2 With Y D2 The aromatic hydrocarbon ring structures contained therein are directly bonded.

[0351] Preferred Y D1 It includes a structure represented by the following formula (A1-1), more preferably Y D1 The structure is represented by equation (A1-1).

[0352] [Chemical Formula 25]

[0353]

[0354] In equation (A1-1), R A11 ~R A16 Each of the following can be independently represented: hydrogen atom, alkyl group, cyclic alkyl group, alkoxy group, hydroxyl group, cyano group, haloalkyl group, or halogen atom. A11 R represents a single bond, carbonyl group, sulfonyl group, divalent saturated hydrocarbon group, divalent unsaturated hydrocarbon group, heteroatom, heterocyclic group, or alkyl halide. A11 ~R A16 At least one of them or L A11 To correspond with P in the above formula (LD-2)D2 The * indicates the bonding sites with other structures, and the * indicates the bonding sites with other structures independently.

[0355] In equation (A1-1), as long as R A11 ~R A16 At least one of them or L A11 To correspond with P in the above formula (LD-2) D2 The bonding site is sufficient, preferably L. A11 To correspond with P in the above formula (LD-2) D2 The bonding sites.

[0356] In equation (A1-1), R A11 ~R A16 Preferably, each of the following is independently represented: hydrogen atom, alkyl group with 1 to 6 carbon atoms, cyclic alkyl group with 3 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, hydroxyl group, cyano group, halogenated alkyl group with 1 to 3 carbon atoms, or halogen atom. From the viewpoint of solvent solubility, hydrogen atom, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, or halogenated alkyl group with 1 to 3 carbon atoms are more preferred, and hydrogen atom or alkyl group with 1 to 6 carbon atoms are even more preferred.

[0357] As mentioned above, R A11 ~R A16 The halogen atom in the aforementioned halogenated alkyl group can be a fluorine atom, chlorine atom, bromine atom, iodine atom, etc., with chlorine atom or bromine atom being preferred.

[0358] In formula (A1-1), L A1 Preferably, P is the same as in the above formula (LD-2). D2 The bonding site. Here, L A1 To correspond with P in the above formula (LD-2) D2 When bonding the L site, A1 Preferably, it is a divalent hydrocarbon group, more preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, especially preferably an aliphatic hydrocarbon group.

[0359] As the aforementioned aliphatic hydrocarbon group, an aliphatic hydrocarbon group with 1 to 10 carbon atoms is preferred, and an aliphatic hydrocarbon group with 1 to 4 carbon atoms is more preferred.

[0360] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 10 carbon atoms is preferred, and an aromatic hydrocarbon group with 6 carbon atoms is more preferred.

[0361] L A1 Not P in equation (LD-2) D2 When bonding the L site, A1 Preferred groups include single bonds, divalent saturated hydrocarbon groups with 1 to 6 carbon atoms, divalent unsaturated hydrocarbon groups with 5 to 24 carbon atoms, -O-, -S-, and -NR.N The R group is a heterocyclic group or a haloalkylene group having 1 to 6 carbon atoms, more preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and even more preferably a single bond or -O-. N As described above.

[0362] -P D2 -

[0363] P D2 Preferably, it is a group represented by the above formula (PD-1).

[0364] -m-

[0365] In formula (LD-2), m represents an integer greater than 2, preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0366] -Synthesis Method-

[0367] For example, the structure represented by the above formula (LD-1) can be obtained as a structure derived from the carboxylic dianhydride represented by the following formula (LDB-1).

[0368] [Chemical Formula 26]

[0369]

[0370] In the above formula (LDB-1), Y D2 P D2 m and Y in the above formula (LD-2) are respectively D2 P D2 The meanings of 'm' and 'm' are the same, and their optimization methods are also the same.

[0371] Furthermore, for example, specific resins can be synthesized by using a carboxylic acid dianhydride having reactive groups such as alkoxy groups to synthesize a resin, and reacting a compound having a structure that reacts with the aforementioned reactive groups to form covalent bonds (e.g., halogenated alkyl groups) and exhibiting the property of producing a base with the aforementioned resin.

[0372] The synthesis method of a specific resin can be selected by taking into account the desired structure of the specific resin, the yield of the specific resin, the ease of synthesis, and the cost related to the raw materials or reaction conditions.

[0373] R in equation (2) 113 and R 114 Each can be represented independently by 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 polyalkoxide group. Furthermore, R is preferred. 113 and R 114At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114 At least one of the polymerizable groups comprises two or more polymerizable groups. The polymerizable group is a group capable of cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl 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 vinyl unsaturated bonds is preferred.

[0374] Examples of groups having vinyl 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.

[0375] [Chemical Formula 27]

[0376]

[0377] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0378] In equation (III), * indicates the bonding site with other structures.

[0379] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0380] 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 polyalkoxide compounds; more preferably, alkylene compounds such as vinyl and propenyl, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as vinyl and propenyl or polyalkoxide compounds.

[0381] In this invention, polyalkoxide refers to a group consisting of two or more alkoxide groups directly bonded together. The alkylene groups within the multiple alkoxide groups of a polyalkoxide group may be the same or different.

[0382] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0383] 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.

[0384] Furthermore, the aforementioned alkylene groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0385] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0386] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethoxy, or groups bonded to multiple ethyleneoxy and multiple propyleneoxy groups are preferred as polyvinyloxy groups, more preferably polyvinyloxy or polypropyleneoxy, and even more preferably polyvinyloxy. 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.

[0387] 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 vinyl unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such tertiary amine compounds having vinyl unsaturated bonds.

[0388] 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.

[0389] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl group, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0390] Moreover, R 113 and R 114 At least one of the structures in the invention contains the above-described structure that exhibits the property of producing an alkali, which is also one of the preferred embodiments of the invention.

[0391] For example, R can be preferred. 113 and R 114 At least one of them is a structure represented by the above formula (1-1) or a structure represented by the above formula (1-2).

[0392] R 113 and R 114 When at least one of the components contains the structure described above that exhibits the property of producing an alkali, the specific resin contains relative to all R 113 and R 114 The R structure, which exhibits the property of producing a base, contains 113 and R 114 The content is preferably 0.1 to 100 mol%, more preferably 0.5 to 50 mol%, and even more preferably 1 to 20 mol%.

[0393] 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.

[0394] 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.

[0395] 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.

[0396] Equation (2-A)

[0397] [Chemical Formula 28]

[0398]

[0399] 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.

[0400] 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.

[0401] R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0402] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). Moreover, it is clear that the polyimide precursor may contain other types of repeating units besides the repeating unit of formula (2) described above.

[0403] 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).

[0404] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0405] 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.

[0406] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0407] 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 when the multiple polyimide precursors are used as a single resin are each within the aforementioned ranges.

[0408] [Polybenzoxazole precursor]

[0409] 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).

[0410] [Chemical Formula 29]

[0411]

[0412] 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.

[0413] When a particular resin contains a repeating unit represented by formula (3), the particular resin preferably contains a structure exhibiting the property of generating an alkali within the repeating unit represented by formula (3), and more preferably contains a structure represented by formula (1-1) above within the repeating unit represented by formula (3).

[0414] For example, R is preferably selected from formula (3). 121 R 122 R 123 and R 124 At least one of the structures contains the structure exhibiting the property of producing an alkali (preferably the structure represented by formula (1-1)), more preferably R selected from formula (3). 123 and R 124 At least one of the structures contains the structure that exhibits the property of producing an alkali (preferably the structure represented by formula (1-1)).

[0415] Furthermore, when a particular resin contains a repeating unit represented by formula (3), the particular resin may contain a structure exhibiting the property of generating an alkali at a location different from the repeating unit represented by formula (3).

[0416] For example, examples include a particular resin having a structure at the end that exhibits the property of producing an alkali, or a particular resin having a repeating unit that is different from the repeating unit represented by formula (3) and has a structure that exhibits the property of producing an alkali.

[0417] 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, it is preferred that at least one of them is a polymeric group.

[0418] 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.

[0419] As a dicarboxylic acid residue, it is preferred to be a dicarboxylic acid containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.

[0420] The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group, more preferably a dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, 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.

[0421] 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, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[0422] [Chemical Formula 30]

[0423]

[0424] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0425] 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.

[0426] [Chemical Formula 31]

[0427]

[0428] 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.

[0429] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

[0430] 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.

[0431] Moreover, R 122Preferably, 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-( 4-Amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

[0432] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic groups are preferred.

[0433] [Chemical Formula 32]

[0434]

[0435] 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). 122 The 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). 122The 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.

[0436] The diaminophenol derivative is preferably a compound represented by formula (As).

[0437] [Chemical Formula 33]

[0438]

[0439] 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.

[0440] [Chemical Formula 34]

[0441]

[0442] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0443] It is considered that in the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R3, would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, and is particularly preferred from the perspective of further improving the effect of increasing the cyclization rate when curing at low temperature.

[0444] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it is possible to maintain high transparency to i-rays and high cyclization rate during low-temperature curing, which is therefore preferred.

[0445] 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, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred, considering the effects of maintaining high transparency to i-rays and high cyclization rate during low-temperature curing while also having sufficient solubility in solvents and being able to obtain a well-balanced polybenzoxazole precursor.

[0446] 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.

[0447] 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, these are not the only examples.

[0448] In addition to the repeating unit of formula (3) above, polybenzoxazole precursors may also contain other types of repeating units.

[0449] 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.

[0450] [Chemical Formula 35]

[0451]

[0452] 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%.

[0453] In equation (SL), as a preferred Z, R in structure b can be cited as an example. 5s and R 6s The 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.

[0454] 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.

[0455] For example, the weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0456] 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.

[0457] 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.

[0458] [Polyamide-imide precursor]

[0459] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2).

[0460] [Chemical Formula 36]

[0461]

[0462] In equation (PAI-2), R 117 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.

[0463] When a particular resin contains a repeating unit represented by formula (PAI-2), the particular resin preferably contains a structure exhibiting the property of generating an alkali within the repeating unit represented by formula (PAI-2), and more preferably contains a structure represented by formula (1-1) above within the repeating unit represented by formula (PAI-2).

[0464] For example, R is preferably selected from formula (PAI-2). 111 R 113 and R 117 At least one of the structures contains the structure exhibiting the property of producing an alkali (preferably the structure represented by formula (1-1)), more preferably R in formula (PAI-2) 113 It contains the structure that exhibits the property of producing an alkali (preferably the structure represented by formula (1-1)).

[0465] Furthermore, when a particular resin contains a repeating unit represented by formula (PAI-2), the particular resin may contain a structure exhibiting alkali-generating properties at a location different from the repeating unit represented by formula (PA1-2).

[0466] For example, examples include a particular resin having a structure at the end that exhibits the property of generating an alkali, or a particular resin further having a repeating unit that is different from the repeating unit represented by formula (PAI-2) and has a structure that exhibits the property of generating an alkali.

[0467] 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.

[0468] As the aforementioned linking group, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0469] 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.

[0470] 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, and all hydrogen atoms may be substituted with halogen atoms; it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0471] 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.

[0472] 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.

[0473] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0474] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

[0475] Examples of halogenable tricarboxylic acid compounds used to manufacture polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0476] These tricarboxylic acid compounds can be used in one or more forms.

[0477] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a tricarboxylic acid compound formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group with 6 to 20 carbon atoms or a tricarboxylic acid compound formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0478] 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, phthalic acid (or phthalic anhydride) and benzoic acid linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide, etc.

[0479] 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).

[0480] 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.

[0481] The polyamide-imide precursor may further contain other repeating units.

[0482] Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0483] [Chemical Formula 37]

[0484]

[0485] In equation (PAI-1), R 116 R represents a divalent organic group. 111 It represents a divalent organic group.

[0486] 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.

[0487] As the aforementioned linking group, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0488] 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.

[0489] 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, and all hydrogen atoms may be substituted with halogen atoms; it is preferred that all hydrogen atoms are substituted with halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0490] 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.

[0491] Moreover, R 116 Preferably, the compounds are derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0492] 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.

[0493] 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.

[0494] 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.

[0495] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0496] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferably a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing 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 containing 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.

[0497] 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, pentacosanedioic 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.

[0498] As a specific example of a dicarboxylic acid dihalide compound, one can cite compounds with a structure in which two carboxyl groups are halogenated, which are specific examples of dicarboxylic acid compounds mentioned above.

[0499] In equation (PAI-1), R 111 R in equation (2) above 111 The meanings are the same, and the preferred selection methods are also the same.

[0500] 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.

[0501] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as the diamine component can be cited.

[0502] 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).

[0503] 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).

[0504] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. 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.

[0505] 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. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that at least one polyamide-imide precursor has a weight-average molecular weight, number-average molecular weight, and dispersion within the above-mentioned ranges. Moreover, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersion calculated when the multiple polyamide-imide precursors are used as a single resin are each within the above-mentioned ranges.

[0506] [Methods for manufacturing polyimide precursors, etc.]

[0507] 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 esterifying it with a condensing agent or alkylating agent; obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; obtaining a diester by 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 by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred.

[0508] Examples of condensing agents include dicyclohexanediimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0509] 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.

[0510] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0511] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0512] 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.

[0513] In methods for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0514] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacerbicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0515] -End- Capping Agent-

[0516] In the manufacture of polyimide precursors, etc., to further improve storage stability, it is preferable to end-cap the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the polyimide precursor, etc. When end-capping the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monools, phenols, thiols, benzenethiophenols, monoamines, etc. Considering reactivity and film stability, monools, phenols, and monoamines are more preferred. Preferred compounds as monools include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as butanol and adamantanol. Preferred compounds among phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Furthermore, preferred compounds among 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.

[0517] Furthermore, when capping the amino group at the lipid terminus, compounds with functional groups capable of reacting with the amino group can be used for capping. Preferred capping agents for the amino group 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, pentanoyl chloride, cyclohexyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarboxyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0518] Furthermore, by using compounds with structures exhibiting alkali-generating properties as end-capping agents, it is possible to introduce structures exhibiting alkali-generating properties into the ends of specific resins.

[0519] As such end-capping agents, for example, compounds having structures exhibiting the property of producing bases and reactive groups such as hydroxyl, thiol, amino, carboxyl, carboxylic anhydride, carboxylic halide acyl, sulfonic anhydride, sulfonic halide acyl, or sulfonic carboxylic anhydride can be utilized.

[0520] As a capping agent, for example, a compound having a structure exhibiting the property of producing more than 1 base and one of the above-mentioned reactive groups can be used.

[0521] The preferred configuration for exhibiting the properties of producing an alkali is as described above.

[0522] -Solid precipitation-

[0523] 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.

[0524] [Specific example]

[0525] As a specific example of a particular resin, there is no particular limitation, but the specific resin used in the embodiments described later can be preferred.

[0526] 〔content〕

[0527] 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.

[0528] 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.

[0529] Furthermore, the resin composition of the present invention preferably contains at least two resins.

[0530] 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.

[0531] When the resin composition of the present invention comprises two or more specific resins, it preferably comprises, for example, a structure derived from dianhydride (R in formula (2) above). 115 Two or more different polyimide precursors.

[0532] <Other Resins>

[0533] 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").

[0534] Other resins include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, polyamide-imides, 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.

[0535] As the aforementioned polyimide precursor, polybenzoxazole precursor, and polyamide-imide precursor, a resin identical to the specific resin described above can be used, except that it does not have a structure exhibiting the property of generating an alkali.

[0536] Furthermore, as the aforementioned polyimide, polybenzoxazole, and polyamide-imide, it is possible to use a resin formed by cyclizing the aforementioned specific resin, or a resin formed by cyclizing the same resin as the aforementioned specific resin except that it does not have a structure exhibiting the property of generating an alkali. In this case, the solubility in the solvent can be considered, and some of the structure can be modified.

[0537] 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.

[0538] For example, by replacing the polymerizable compound described later in the resin composition or by adding a polymerizable compound with a weight average molecular weight of less than 20,000 and a high polymerizable group value (e.g., the molar amount of polymerizable groups in 1g of resin is 1×10⁻⁶) in addition to the polymerizable compound described later. -3 (Meth)acrylic resins with a molar ratio of 100 mol / g or higher can improve the coatability of resin compositions, solvent resistance of patterns (cured products), etc.

[0539] 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.

[0540] 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.

[0541] 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.

[0542] 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.

[0543] Organometallic complexes

[0544] From the viewpoint of drug resistance, the resin composition of the present invention may contain organometallic complexes.

[0545] Organometallic complexes are any organic complex compounds containing metal atoms, preferably complex compounds containing metal atoms and organic groups, more preferably compounds in which organic groups are coordinated with metal atoms, and even more preferably metallocene compounds.

[0546] In this invention, metallocene compounds refer to organometallic complexes containing two cyclopentadienyl anionic derivatives that may have substituents as η5-ligands.

[0547] The organic group mentioned above is not particularly limited, but a hydrocarbon group or a group composed of a hydrocarbon group and a heteroatom is preferred. As for the heteroatom, oxygen atom, sulfur atom, and nitrogen atom are preferred.

[0548] In this invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferably at least two of them are cyclic groups.

[0549] The aforementioned cyclic group is preferably selected from 5-membered ring cyclic groups and 6-membered ring cyclic groups, and more preferably from 5-membered ring cyclic groups.

[0550] The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, but is preferably a hydrocarbon ring.

[0551] As a cyclic group of a 5-membered ring, cyclopentadienyl is preferred.

[0552] Furthermore, the organometallic complexes used in this invention preferably contain 2 to 4 cyclic groups per molecule.

[0553] The metal included in the organometallic complex is not particularly limited, but preferably a metal equivalent to a Group 4 element, more preferably at least one metal selected from titanium, zirconium and hafnium, even more preferably at least one metal selected from titanium and zirconium, and especially preferably titanium.

[0554] Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, preferably only one metal atom. When organometallic complexes contain two or more metal atoms, they can contain only one type of metal atom or two or more types of metal atoms.

[0555] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, more preferably a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, even more preferably a titanocene compound or a zirconium diacene compound, and especially preferably a titanocene compound.

[0556] The ability of organometallic complexes to initiate photoradical polymerization is also one of the preferred methods of this invention.

[0557] In this invention, the ability to initiate photoradical polymerization refers to the ability to generate free radicals capable of initiating free radical polymerization through light irradiation. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation ability can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it has disappeared, an appropriate method can be selected according to the type of free radical crosslinking agent, such as IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography).

[0558] When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, even more preferably a titanocene compound or a zirconium diacene compound, and especially preferably a titanocene compound.

[0559] When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably selected from at least one compound selected from titanium diacene compounds, tetraalkoxy titanium compounds, acylated titanium compounds, chelated titanium compounds, zirconium diacene compounds, and hafnium diacene compounds; more preferably selected from at least one compound selected from titanium diacene compounds, zirconium diacene compounds, and hafnium diacene compounds; even more preferably selected from at least one compound selected from titanium diacene compounds and zirconium diacene compounds; and especially preferably titanium diacene compounds.

[0560] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0561] As organometallic complexes, compounds represented by the following formula (P) are preferred examples.

[0562] [Chemical Formula 38]

[0563]

[0564] In formula (P), M is a metal atom, and R are independent substituents.

[0565] The R mentioned above is preferably selected independently from aromatic groups, alkyl groups, halogen atoms and alkyl sulfonyloxy groups.

[0566] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, even more preferably a titanium atom or a zirconium atom, and especially preferably a titanium atom.

[0567] As an aromatic group in R in formula (P), examples include aromatic groups with 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups with 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl.

[0568] As for the alkyl group in formula (P), it is preferably an alkyl group with 1 to 20 carbon atoms, and more preferably an alkyl group with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc.

[0569] Examples of halogen atoms in R include F, Cl, Br, and I.

[0570] As the alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R, it is preferably an alkyl group with 1 to 20 carbon atoms, and more preferably an alkyl group with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc.

[0571] The R group mentioned above can further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0572] Specific examples of organometallic complexes are not particularly limited, and examples include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, diisopropoxybis(acetylacetone) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadientrimethoxy titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, and the following compounds.

[0573] [Chemical Formula 39]

[0574]

[0575] In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may be used, but are not limited thereto.

[0576] The content of the organometallic complex relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0577] One or more organometallic complexes can be used. When two or more are used, the total amount is preferably within the range mentioned above.

[0578] <Polymerizing compounds>

[0579] The resin composition of the present invention preferably contains a polymerizable compound.

[0580] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0581] [Free radical crosslinking agent]

[0582] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0583] 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 ethylene unsaturated bond. Examples of such groups containing an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido groups.

[0584] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred as the groups containing ethylene unsaturated bonds, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0585] The free radical crosslinking agent is preferably a compound having one or more vinyl unsaturated bonds, more preferably a compound having two or more vinyl unsaturated bonds. The free radical crosslinking agent may have three or more vinyl unsaturated bonds.

[0586] As for the above-mentioned compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred.

[0587] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains compounds having two ethylene unsaturated bonds and compounds having three or more of the above-mentioned ethylene unsaturated bonds.

[0588] 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.

[0589] 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. Furthermore, 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.

[0590] 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 and then reacted with ethylene oxide or propylene oxide followed by (meth)propylene. The compounds include 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; polyfunctional acrylates or methacrylates such as epoxy acrylates, which are products of the reaction between epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are preferred. Also, examples include polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and vinyl unsaturated bonds, such as glycidyl (meth)acrylate.

[0591] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a fluorene ring and containing two or more groups with ethylene 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.

[0592] 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.

[0593] 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.

[0594] Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then esterifying it with (meth)acrylate, as 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.

[0595] 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.

[0596] As free radical crosslinking agents, preferred products include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. Other oligomer types can also be used.

[0597] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methacrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentyloyl groups manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyloyl 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 Co., Ltd.). Products manufactured by Kayaku Co., Ltd. include UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and BLEMMER PME400 (manufactured by NOFCORPORATION.).

[0598] 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.

[0599] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. Among free radical crosslinking agents having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical crosslinking agents that have acid groups by reacting the unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Particularly preferred are free radical crosslinking agents that have acid groups by reacting the unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, wherein the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. As commercially available products, examples include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0600] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid value was measured according to the description in JIS K 0070:1992.

[0601] From the viewpoint of pattern resolution and film elasticity, difunctional methacrylates or acrylates are preferably used in the resin composition.

[0602] 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, and 1,6-hexanediol can be used. Dimethacrylate, dimethyloltricyclodecane dimethacrylate, dimethyloltricyclodecane dimethacrylate, ethylene oxide (EO) adduct of bisphenol A dimethacrylate, PO adduct of bisphenol A dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified dimethacrylate of isocyanuric acid, isocyanuric acid-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0603] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0604] From the viewpoint of suppressing warping that accompanies the control of the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are (meth)acrylate n-butyl acrylate, (meth)acrylate 2-ethylhexyl acrylate, (meth)acrylate 2-hydroxyethyl acrylate, (meth)acrylate butoxyethyl acrylate, (meth)acrylate carbitol acrylate, (meth)acrylate cyclohexyl acrylate, (meth)acrylate benzyl acrylate, (meth)acrylate phenoxyethyl acrylate, N-hydroxymethyl (meth)acrylamide, (meth)acrylate glycidyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, and allyl glycidyl ether. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at ambient pressure are also preferred.

[0605] 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.

[0606] 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.

[0607] 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.

[0608] [Other crosslinking agents]

[0609] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0610] In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, it is a compound having a plurality of groups within its molecule that promote the formation of covalent bonds between itself and other compounds in the composition or their reaction products by means of the aforementioned photoacid generator or photobase generator. More preferably, it is a compound having a plurality of groups within its molecule that promote the formation of covalent bonds between itself and other compounds in the composition or their reaction products by means of the action of an acid or base.

[0611] 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.

[0612] 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.

[0613] Other crosslinking agents include, for example, compounds having a structure obtained by reacting amino-containing compounds such as melamine, glycourea, urea, alkylene urea, and benzoguanidine with formaldehyde, or by reacting formaldehyde with an alcohol and replacing the hydrogen atoms of the amino group 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.

[0614] As for the aforementioned amino-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycourea, 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.

[0615] In these, 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 urea-based crosslinking agents and melamine-based crosslinking agents described later.

[0616] As a compound containing at least one of alkoxymethyl and acylmethyl groups in this invention, examples of its structure include compounds in which the alkoxymethyl or acylmethyl group is directly substituted on the nitrogen atom of an aromatic group or a urea structure described below, or on a triazine.

[0617] Regarding the alkoxymethyl or acylmethyl groups present in the above-mentioned compounds, it is preferred that the number of carbon atoms is 2 to 5, more preferably 2 or 3, and even more preferably 2.

[0618] 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.

[0619] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0620] [Chemical Formula 40]

[0621]

[0622] R 100 Indicates alkyl or acyl groups.

[0623] 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.

[0624] Compounds in which alkoxymethyl or acylmethyl groups are directly substituted on an aromatic group include, for example, compounds of the following general formula.

[0625] [Chemical Formula 41]

[0626]

[0627] 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.

[0628] 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.

[0629] 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 (OR) 39 )wait.

[0630] 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.

[0631] 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.

[0632] The aforementioned alkyl groups can be either straight-chain or branched.

[0633] 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.

[0634] The aforementioned cycloalkyl groups can be monocyclic structures or polycyclic structures such as fused rings.

[0635] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0636] As the aforementioned aralkyl group, aralkyl groups with 7 to 20 carbon atoms are preferred, and alkyl groups with 7 to 16 carbon atoms are more preferred.

[0637] 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.

[0638] 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.

[0639] Moreover, these groups can further have known substituents within the scope of achieving the effects of the present invention.

[0640] 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.

[0641] 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.

[0642] 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.

[0643] [Chemical Formula 42]

[0644]

[0645] [Chemical Formula 43]

[0646]

[0647] For compounds containing at least one of alkoxymethyl and acylmethyl, commercially available products can be used, as well as compounds synthesized by known methods.

[0648] 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.

[0649] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0650] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monoethoxymethylated glycourea, diethoxymethylated glycourea, triethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc.

[0651] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0652] 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.

[0653] 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.

[0654] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0655] 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.

[0656] 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).

[0657] 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.

[0658] 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.

[0659] 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.

[0660] -Epoxy compounds (compounds containing epoxy groups)-

[0661] 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, the low-temperature curing and warpage of the resin composition of the present invention can be effectively suppressed.

[0662] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide indicates that the number of repeating units in the ethylene oxide is 2 or more, preferably 2 to 15.

[0663] 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 polysiloxanes containing epoxy groups such as polymethyl(epoxypropoxypropyl)siloxane, but 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 Chemical 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.

[0664] [Chemical Formula 44]

[0665]

[0666] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0667] In the above structure, considering both heat resistance and improved elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[0668] -Oxybutane compounds (compounds containing oxybutane groups)-

[0669] 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)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane)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.

[0670] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0671] 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.

[0672] 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 phenolic varnish-type dihydrobenzoxazine compounds. These can be used alone or in combination of two or more.

[0673] 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 thermal crosslinking agents are present, their total content is preferably within the above-mentioned range.

[0674] [Polymerization initiator]

[0675] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. Particularly preferred is a photopolymerization initiator.

[0676] 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, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can be an active agent that generates active free radicals by interacting with a photoexcited sensitizer.

[0677] 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 can be measured using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer), preferably with ethyl acetate as solvent, at a concentration of 0.01 g / L.

[0678] 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, azide 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.

[0679] 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.

[0680] 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-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as described herein.

[0681] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0682] 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.

[0683] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which match the maximum absorption wavelength with a light source of wavelengths such as 365 nm or 405 nm, can also be used, as this specification is included.

[0684] 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.

[0685] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0686] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, the exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0687] 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.

[0688] 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 linker >C=NOC(=O)-.

[0689] [Chemical Formula 45]

[0690]

[0691] 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.

[0692] [Chemical Formula 46]

[0693]

[0694] 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.

[0695] 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.

[0696] 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.

[0697] 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.

[0698] 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.

[0699] 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.

[0700] 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 being preferred. Acyl is more preferred for the ease of forming a film with excellent lightfastness, and benzoyl is even more preferred. Benzoyl may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, or amino being more preferred, and alkoxy, alkylthioalkyl, or amino being even more preferred.

[0701] 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).

[0702] [Chemical Formula 47]

[0703]

[0704] 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.

[0705] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0706] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0707] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0708] In the above formula, R is preferred. X12 R is an electron-withdrawing group. X10 R X11 R X13 R X14 It is a hydrogen atom.

[0709] 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.

[0710] Examples of preferred oxime compounds include those with specific substituents disclosed in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups disclosed in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0711] 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.

[0712] 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.

[0713] 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-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1; quinones formed by cyclization of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. Moreover, compounds represented by the following formula (I) can also be used.

[0714] [Chemical Formula 48]

[0715]

[0716] 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.

[0717] [Chemical Formula 49]

[0718]

[0719] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0720] 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.

[0721] As photoradical polymerization initiators, photoradical 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. Furthermore, 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.

[0722] 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.

[0723] In addition, photopolymerization initiators can sometimes also act as thermal polymerization initiators. Therefore, heating with ovens, heating plates, etc., can sometimes further promote crosslinking based on photopolymerization initiators.

[0724] [Sensitizer]

[0725] 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.

[0726] As usable sensitizers, compounds such as benzophenone, mifepristone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0727] 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.

[0728] Furthermore, sensitizing pigments can also be used.

[0729] For details regarding the sensitizing pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0730] 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.

[0731] [Chain transfer agent]

[0732] 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, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl sulfides 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.

[0733] 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.

[0734] 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.

[0735] <Alkali generating agent>

[0736] 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.

[0737] 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, the cyclization reaction of the precursor can be promoted by heating, thereby improving the mechanical properties and chemical resistance of the cured product, such as improving the performance of the interlayer insulating film used as a rewiring layer in semiconductor packaging.

[0738] 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.

[0739] The alkali generating agent of the present invention is not particularly limited, 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 acyloxyimide compounds.

[0740] Specific compounds that can be cited as nonionic base generating agents include those represented by formula (B1), formula (B2), or formula (B3).

[0741] [Chemical Formula 50]

[0742]

[0743] 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 2 and 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 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.

[0744] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3At 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.

[0745] More specifically, Rb 1 and Rb 2 Preferably, the groups are hydrogen atoms, alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), or aralkyl groups (preferably 7-25 carbon atoms, more preferably 7-19, and even more preferably 7-12). These groups may have substituents within the range that allows the effects of the invention to be achieved. 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 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 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.

[0746] As Rb 3 Examples of such compounds include alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-12, and even more preferably 2-6), aralkyl groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), aryl-alkenyl groups (preferably 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16), alkoxy groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryloxy groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or arylalkoxy groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12). Among them, cycloalkyl (preferably 3-24 carbon atoms, more preferably 3-18, and even more preferably 3-12), aryl, and arylalkoxy are preferred. Rb 3 The invention may further contain substituents within the scope of achieving the effects of the invention.

[0747] The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

[0748] [Chemical Formula 51]

[0749]

[0750] 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.

[0751] Rb 13 The groups are alkyl (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, and 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.

[0752] Rb 33 and Rb 34 Each 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), with hydrogen atoms being the most preferred.

[0753] 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.

[0754] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0755] [Chemical Formula 52]

[0756]

[0757] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 They have the same meaning.

[0758] Rb 15 and Rb 16 The atom is hydrogen, alkyl (preferably 1-12 carbon atoms, more preferably 1-6, and even more preferably 1-3), alkenyl (preferably 2-12 carbon atoms, more preferably 2-6, and even more preferably 2-3), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-11), and preferably hydrogen or methyl.

[0759] 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), and aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), with aryl being the most preferred.

[0760] [Chemical Formula 53]

[0761]

[0762] In formula (B3), L represents a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the linking chain path. Furthermore, R... N1 and R N2 Each can be used to represent a monovalent organic group independently.

[0763] In this specification, "linking chain" refers to an atomic chain that connects two atoms or groups of atoms along a path that links them with the shortest possible distance (minimum number of atoms). For example, in a compound represented by the following formula, L is composed of styrene, has a vinyl group 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 "linking chain length" or "linking chain length") is 4.

[0764] [Chemical Formula 54]

[0765]

[0766] The number of carbon atoms in L in 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 facilitating the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 5 or less. The linking chain length of L is especially 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.

[0767] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0768] [Chemical Formula 55]

[0769]

[0770] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 It represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0771] L is a divalent linker, preferably a divalent organic group. The linker chain length 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 linker 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.

[0772] In equation (N1), R N1 and R N2 Each group 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 N2If an aliphatic hydrocarbon group is used, the resulting base will have high basicity and is 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 aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0773] 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 number of carbon atoms in the straight-chain or branched chain alkyl group is preferably 1 to 24, 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.

[0774] The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0775] The number of carbon atoms in the group involved in the combination of chain alkyl and cyclic alkyl is preferably 4 to 24, 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 include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0776] The alkyl group having 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 having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0777] 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 or alkyl groups having 1 to 8 carbon atoms are preferred.

[0778] 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 N2The 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, pyrazoleidine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings being particularly preferred.

[0779] R C1 This indicates a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0780] As a protecting group, a protecting group that decomposes by the action of an acid or base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0781] 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.

[0782] The divalent linker 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 linker 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.

[0783] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group (e.g., arylene alkyl) involved in the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0784] As the linking group L, specifically, preferably a linear or branched chain alkylene, a cyclic alkylene, a combination of a linear alkylene and a cyclic alkylene, an alkylene with an oxygen atom in the chain, a linear or branched chain alkenyl, a cyclic alkenyl, an aryl, or an aryl alkylene.

[0785] 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.

[0786] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0787] The number of carbon atoms in the groups involved in the combination of chain alkylene and cyclic alkylene is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0788] The alkylene group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. The number of carbon atoms in the alkylene group containing oxygen atoms in the chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0789] The number of carbon atoms in the linear or branched chain-like alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0790] 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.

[0791] The number of carbon atoms in the arylene group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10.

[0792] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0793] 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).

[0794] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting thereto.

[0795] [Chemical Formula 56]

[0796]

[0797] 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.

[0798] 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.

[0799] Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto.

[0800] [Chemical Formula 57]

[0801]

[0802] Specific examples of imine salts include the following compounds, but the present invention is not limited thereto.

[0803] [Chemical Formula 58]

[0804]

[0805] 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 the 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, but can be 5 parts by weight or less, or even 4 parts by weight or less.

[0806] 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.

[0807] Solvent

[0808] The resin composition of the present invention preferably contains a solvent.

[0809] 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.

[0810] 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, δ-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 2-alkoxypropionate esters (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.

[0811] 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 acetate cellosolve, ethyl acetate cellosolve, 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.

[0812] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0813] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0814] As a sulfoxide, dimethyl sulfoxide is preferably used, for example.

[0815] 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.

[0816] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0817] 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.

[0818] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0819] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 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.

[0820] 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.

[0821] 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.

[0822] <Metal Adhesion Modifier>

[0823] 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.

[0824] [Silane coupling agent]

[0825] 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.

[0826] [Chemical Formula 59]

[0827]

[0828]

[0829] 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.

[0830] [Aluminum-based adhesive additives]

[0831] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0832] 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.

[0833] 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.

[0834] <Migration Inhibitor>

[0835] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0836] There are no particular limitations on the migration inhibitors, and 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, pyrazine 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 derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0837] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0838] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0839] The following compounds can be cited as specific examples of migration inhibitors.

[0840] [Chemical Formula 60]

[0841]

[0842] 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.

[0843] 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.

[0844] <Polymerization Inhibitor>

[0845] 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.

[0846] Preferred compounds as polymerization inhibitors include hydroquinone, catechol, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallnutol, 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, 1-nitroso-2-naphthol, 2-nitroso- 1-Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-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, phenanthridine, phenoxazine, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, aluminum N-nitroso-N-phenylhydroxyamine, ammonium N-nitroso-N-phenylhydroxyamine, 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.

[0847] 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.

[0848] 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.

[0849] <Other Additives>

[0850] The resin composition of the present invention can be incorporated with various additives as needed within the scope of achieving the effects of the present invention, such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other additives (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the properties of the film and other properties can be adjusted. Regarding these components, for example, reference can be made to paragraphs 0183 onwards in 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 less than 3% by mass of the solid components of the resin composition of the present invention.

[0851] [surfactants]

[0852] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0853] 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 composition containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to further preferably form a film with a uniform thickness and small thickness non-uniformity.

[0854] 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, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, 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 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.

[0855] Fluorinated surfactants may also preferably use fluorinated polymers (comprising 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), and the following compounds may also be cited as fluorinated surfactants used in this invention.

[0856] [Chemical Formula 61]

[0857]

[0858] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0859] Regarding fluorinated surfactants, fluoropolymers with vinyl 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-7 18K manufactured by DICCOporation.

[0860] 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 and liquid-saving properties, and also have good solubility in the composition.

[0861] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (manufactured by Shin-EtsuChemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0862] 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).

[0863] 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 stearate, 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 PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by 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.

[0864] As cationic surfactants, examples include organosiloxane polymers such as KP-341 (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.).

[0865] As anionic surfactants, examples include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0866] Surfactants can be used in single-agent or in combination of two or more.

[0867] 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.

[0868] [Higher fatty acid derivatives]

[0869] 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.

[0870] 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.

[0871] 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 there may be 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.

[0872] [Thermal polymerization initiator]

[0873] 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, initiating or promoting the polymerization reaction of a polymerizable compound. 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.

[0874] 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.

[0875] 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.

[0876] [Inorganic particles]

[0877] 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.

[0878] The average particle size of the aforementioned inorganic particles is preferably 0.01–2.0 μm, more preferably 0.02–1.5 μm, even more preferably 0.03–1.0 μm, and particularly preferably 0.04–0.5 μm.

[0879] 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 based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0880] If the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation light transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0881] [Ultraviolet absorber]

[0882] 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.

[0883] 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.

[0884] 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.

[0885] In this invention, the various ultraviolet absorbers mentioned above can be used individually or in combination of two or more.

[0886] 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.

[0887] [Organotitanium compounds]

[0888] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0889] As usable organotitanium compounds, examples include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0890] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0891] 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.

[0892] 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.

[0893] 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.

[0894] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0895] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0896] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0897] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0898] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the above-mentioned I) chelated titanium compound, II) tetraalkoxy titanium compound, and III) dicarboxylated titanium compound is preferred as the organotitanium compound. Particularly preferred are 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.

[0899] 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 resulting cured pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount is 10 parts by weight or less, the composition exhibits better storage stability.

[0900] [Antioxidants]

[0901] 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, antioxidants are also preferably compounds 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]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-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 ADEKACORPORATION). 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. As potential antioxidants, examples include compounds in which the site where the antioxidant function is protected by a protecting group, in which the protecting group is removed by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst, thereby functioning as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available examples of potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKACORPORATION).

[0902] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0903] [Chemical Formula 62]

[0904]

[0905] 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.

[0906] The compound represented by formula (3) inhibits the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups present in the resin. Moreover, it can inhibit metal oxidation by preventing rust on metal materials.

[0907] 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 groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and these groups may further have substituents. From the viewpoint of solubility in the developer and metal adhesion, alkyl ethers and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion based on metal complexation, -NH- is more preferred.

[0908] The following compounds are examples of compounds represented by general formula (3), but are not limited to the following structures.

[0909] [Chemical Formula 63]

[0910]

[0911] [Chemical Formula 64]

[0912]

[0913] [Chemical Formula 65]

[0914]

[0915] [Chemical Formula 66]

[0916]

[0917] The amount of antioxidant added relative to the 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 the effects of tensile properties and improved adhesion to metal materials, even under high temperature and high humidity environments. Moreover, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, their total amount is preferably within the above-mentioned range.

[0918] [Anticoagulant]

[0919] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0920] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[0921] 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.

[0922] [Phenolic compounds]

[0923] 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 CORPORATION).

[0924] In this invention, phenolic compounds can be used alone or in combination of two or more.

[0925] 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.

[0926] [Other polymers]

[0927] 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 modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0928] In this invention, other polymer compounds can be used alone or in combination of two or more.

[0929] 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.

[0930] <Characteristics of Resin Compositions>

[0931] 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. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to apply the required film thickness for the insulating film used in rewiring. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0932] <Restrictions on substances contained in resin compositions>

[0933] 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. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0934] Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the container during storage.

[0935] 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.

[0936] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0937] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The content existing in the form of 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 bromide ions, is preferably within the above-mentioned ranges.

[0938] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0939] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, to prevent impurities from contaminating the raw materials or the resin composition of the present invention, it is preferable to use a multi-layer bottle whose inner wall is composed of six layers of six different resins, or a bottle in which the six resins are formed into a seven-layer structure. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0940] <Cure of the resin composition>

[0941] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0942] The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

[0943] The curing of the resin composition is preferably carried out by heating, with the heating temperature 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 it 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, or 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.

[0944] 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.

[0945] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0946] <Characteristics of cured resin compositions>

[0947] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0948] 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.

[0949] 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.

[0950] <Preparation of Resin Compositions>

[0951] 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.

[0952] Mixing can be achieved through methods such as mixing based on stirring blades, mixing based on ball mills, and mixing by rotating the tank itself.

[0953] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0954] 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 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.

[0955] Besides using filters for filtration, impurities can also be removed using adsorbent materials. Furthermore, filtration and impurity removal using adsorbent materials can be combined. Known adsorbent materials can be used as adsorbents. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[0956] After filtration, a further step can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0957] (Method for manufacturing solidified products)

[0958] The method for manufacturing the cured product of the present invention includes: a film forming step, wherein a film is formed on a substrate by applying a resin composition comprising a precursor of a cyclized resin; an exposure step, wherein the film is selectively exposed; a developing step, wherein the film is developed using a developing solution to form a pattern; and a heating step, wherein the pattern is heated at a temperature of 50°C or higher and 250°C or lower, wherein the precursor of the cyclized resin is a compound that generates an alkali in the heating step.

[0959] As a precursor of the cyclized resin used in the method for manufacturing the cured product of the present invention, specific resins included in the resin composition of the present invention described above are preferably examples.

[0960] Furthermore, the resin composition used in the film formation step of the method for manufacturing the cured product of the present invention is preferably the resin composition of the present invention described above.

[0961] The following is a detailed explanation of each process.

[0962] <Membrane Formation Process>

[0963] The resin composition of the present invention can be used in a film forming process in which it is applied to a substrate to form a film.

[0964] The method for manufacturing the cured product of the present invention includes a film forming step of applying a resin composition to a substrate to form a film.

[0965] [Substrate]

[0966] The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal or substrates with metal layers formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0967] Furthermore, layers such as a sealing layer and an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0968] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[0969] As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the shorter side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

[0970] Furthermore, as a substrate, a plate-like material can be used, with a panel-like substrate (substrate) being preferred.

[0971] Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer composed of cured material) or a metal layer to form a film, the resin layer or the metal layer becomes a substrate.

[0972] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0973] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating are more preferred. From both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0974] Furthermore, it is also possible to apply a method for transferring a coating formed by pre-applying it to a temporary support using the above-described application method onto a substrate.

[0975] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 is also preferred in this invention.

[0976] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0977] Furthermore, the following pre-wetting process can also be used: before coating the resin composition onto the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0978] <Drying Process>

[0979] The above-mentioned membrane can be dried after the membrane formation process (layer formation process) to remove the solvent.

[0980] That is, the method for manufacturing the cured product of the present invention may include a step of drying the film formed by the film forming process.

[0981] Furthermore, the aforementioned drying process is preferably performed after the film formation process and before the exposure process.

[0982] The drying temperature of the membrane in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Furthermore, drying can be carried out by reducing pressure. Examples of drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0983] From the viewpoint of the rectangularity of the cured product, in the film formed in the above-mentioned film forming process, the ratio of the concentration X of the alkali-generating group in the upper 50% of the film thickness direction to the concentration Y of the alkali-generating group in the lower 50% is preferably 0.90 < X / Y < 1.10.

[0984] Based on this method, it is speculated that alkali is easily generated in a near-uniform state within the membrane, for example, a pattern of cured material with excellent rectangularity can be obtained.

[0985] The aforementioned alkali-generating group includes both the structure contained in a specific resin that exhibits alkali-generating properties and the structure contained in the aforementioned alkali-generating agent that exhibits alkali-generating properties. Furthermore, when a compound containing a structure exhibiting alkali-generating properties exists as another compound, that structure is also included in the alkali-generating group.

[0986] From the viewpoint of the rectangularity of the cured material, the X / Y ratio is preferably 0.92 < X / Y < 1.08, and more preferably 0.94 < X / Y < 1.06.

[0987] The above X / Y can be measured by the method described in the embodiments below.

[0988] <Exposure Process>

[0989] The above-mentioned film is used in an exposure process for selective exposure of the film.

[0990] That is, the method for manufacturing the cured product of the present invention includes an exposure step of selectively exposing the film formed by the film forming step.

[0991] Selective exposure refers to exposing only a portion of a film. Furthermore, selective exposure creates exposed areas (exposed areas) and unexposed areas (non-exposed areas) on the film.

[0992] Regarding the exposure amount, there is no particular limitation as long as it is sufficient to cure the resin composition of the present invention. For example, based on the exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm. 2 More preferably 200–8,000 mJ / cm 2 .

[0993] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0994] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of gamma, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is even more preferred. As a result, particularly high exposure sensitivity can be obtained.

[0995] Moreover, the exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure based on direct laser imaging.

[0996] <Post-exposure heating process>

[0997] The above-mentioned film can be used in the heating process after exposure (post-exposure heating process).

[0998] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0999] The post-exposure heating process can be performed after the exposure process and before the development process.

[1000] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[1001] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1002] Regarding the heating rate in the post-exposure heating process, it is preferably 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[1003] Moreover, the heating rate can be adjusted appropriately during the heating process.

[1004] There are no particular limitations on the heating method used in the post-exposure heating process; known heating plates, ovens, infrared heaters, etc., can be used.

[1005] Furthermore, during heating, it is preferable to use inert gases such as nitrogen, helium, or argon to conduct the process in an environment with low oxygen concentration.

[1006] <Developing Process>

[1007] The exposed film is then used in a developing process to form a pattern by developing it with a developing solution.

[1008] That is, the method for manufacturing the cured product of the present invention includes a developing step of developing a film exposed by an exposure step using a developing solution to form a pattern. By developing, one of the exposed and unexposed portions of the film is removed, thereby forming a pattern.

[1009] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[1010] [Developing solution]

[1011] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[1012] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total amount of developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[1013] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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., 3-alkyl...). Methyl hydroxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (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., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferred examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acetate cellosolve, ethyl acetate cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[1014] Furthermore, when the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred; a developer containing at least one selected from cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is most preferred.

[1015] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[1016] The developer may further contain other ingredients.

[1017] Other components include, for example, well-known surfactants and well-known defoamers.

[1018] [Method for supplying developer]

[1019] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous supply of developer. There are no particular restrictions on the type of nozzle; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles.

[1020] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer using a direct current nozzle or a method of continuous supply using a spray nozzle is preferred. From the viewpoint of developer penetration into the image area, a method of supplying developer using a spray nozzle is more preferred.

[1021] Furthermore, the following process can be adopted: after continuously supplying developer with a DC nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a DC nozzle again, rotating the substrate to remove developer from the substrate. This process can also be repeated multiple times.

[1022] Furthermore, as a method for supplying developer in the developing process, one can employ a process of continuously supplying developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer on the substrate using ultrasound or the like, and a process combining these methods.

[1023] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution is not particularly limited, and can be carried out preferably at 10 to 45°C, more preferably at 18 to 30°C.

[1024] In the developing process, pattern cleaning (rinsing) based on rinsing solution can be performed after treatment with developer. Furthermore, methods such as supplying rinsing solution before the developer in contact with the pattern has completely dried can also be employed.

[1025] [Rinse solution]

[1026] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[1027] When the rinsing solution contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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., 3-alkyl...). Methyl hydroxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (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., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferred examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acetate cellosolve, ethyl acetate cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[1028] When the rinsing solution contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[1029] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains at least 50% by mass of an organic solvent, more preferably at least 70% by mass, and even more preferably at least 90% by mass. Furthermore, the rinsing solution may contain 100% by mass of organic solvent.

[1030] The rinsing solution may further contain other ingredients.

[1031] Other components include, for example, well-known surfactants and well-known defoamers.

[1032] [Method for supplying flushing fluid]

[1033] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. The following methods are available: immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by swirling and immersion, supplying the rinsing liquid to the substrate by spraying a nozzle, or continuously supplying the rinsing liquid to the substrate by a direct current nozzle.

[1034] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, direct current nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a mist nozzle supply method is even more preferred. There are no particular limitations on the type of nozzle; examples include direct current nozzles, spray nozzles, and mist nozzles.

[1035] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film using a DC nozzle, and more preferably a process of supplying rinsing liquid using a spray nozzle.

[1036] Furthermore, as a method for supplying rinsing fluid in the rinsing process, one can employ a process of continuously supplying rinsing fluid to the substrate, a process of keeping the rinsing fluid on the substrate in a substantially static state, a process of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a process combining these methods.

[1037] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly limited, and can be preferably 10 to 45°C, more preferably 18 to 30°C.

[1038] From the viewpoint of elongation at break of the cured product, for the film after the exposure process and before the development process, the ratio F / E of the number of moles of alkali-generating groups present in the film as the residual pattern after the development process to the number of moles of alkali-generating groups present in the pattern after the development process is preferably greater than 0.9.

[1039] It is believed that this method can suppress the reduction of alkali-generating groups caused by development and easily obtain cured products with excellent elongation at break.

[1040] Here, regarding the film after the exposure process and before the aforementioned development process, the film remaining as the aforementioned pattern after the development process refers to the portion of the film remaining after development. If it is negative development, the exposed portion corresponds to that portion; if it is positive development, the unexposed portion corresponds to that portion.

[1041] The aforementioned alkali-generating group includes both the structure contained in a specific resin that exhibits alkali-generating properties and the structure contained in the aforementioned alkali-generating agent that exhibits alkali-generating properties. Furthermore, when a compound containing a structure exhibiting alkali-generating properties exists as another compound, that structure is also included in the alkali-generating group.

[1042] From the viewpoint of the elongation at break of the cured product, the F / E ratio is preferably 0.92 or higher, more preferably 0.94 or higher. There is no particular upper limit to the F / E ratio; for example, it can be set to 5.0 or lower. For example, the content of alkali-generating groups after the developing or rinsing process can be increased by including at least one of the developing and rinsing solutions containing an alkali-generating agent, or by contacting the pattern with a treatment solution containing an alkali-generating agent after developing or rinsing.

[1043] The aforementioned F / E can be measured by the method described in the embodiments below.

[1044] <Heating Process>

[1045] The pattern obtained by the developing process (or the washed pattern if a rinsing process is performed) is used in a heating process of the pattern obtained by the developing process, which is heated at a temperature of 50°C or higher and 250°C or lower.

[1046] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[1047] Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[1048] During the heating process, resins such as polyimide precursors cyclize into resins such as polyimide.

[1049] Furthermore, it also involves crosslinking unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins.

[1050] The heating temperature (maximum heating temperature) in the heating process is preferably 50-250°C, more preferably 150-350°C, even more preferably 150-250°C, and even more preferably 160-250°C, especially preferably 160-230°C.

[1051] The heating temperature can be appropriately set to the temperature at which alkali is generated from a specific resin.

[1052] The heating process is preferably the following: by using the action of an alkali or the alkali-generating agent produced from the above-mentioned specific resin or the above-mentioned alkali-generating agent, the cyclization reaction of the above-mentioned polyimide precursor is promoted within the above-mentioned pattern.

[1053] Regarding the heating process, the heating is preferably performed at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. B...

Claims

1. A resin composition comprising a precursor of a cyclized resin, The precursor of the cyclized resin is a precursor of a cyclized resin that produces an alkali when heated to 250°C. The precursor of the cyclized resin comprises at least one repeating unit selected from the following formula (2), repeating unit represented by formula (3), and repeating unit represented by formula (PAI-2). 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 independently represent a hydrogen atom or a monovalent organic group, R 111 R 115 R 113 and R 114 At least one of them contains a structure represented by the following equation (1-1), In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can independently represent a hydrogen atom or a monovalent organic group, R 121 R 122 R 123 and R 124 At least one of them contains a structure represented by the following equation (1-1), In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 R represents a hydrogen atom or a monovalent organic group. 117 R 111 and R 113 At least one of them contains a structure represented by the following equation (1-1), In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 Optional connections form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

2. The resin composition according to claim 1, wherein, During the heating process, the alkali is released from the precursor of the cyclized resin.

3. The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.

4. The resin composition according to claim 1 or 2, further comprising a polymerizable compound.

5. The resin composition according to claim 1 or 2, further comprising an alkali-generating agent.

6. The resin composition according to claim 1 or 2, used for forming an interlayer insulating film for a rewiring layer.

7. A cured product formed by curing the resin composition according to any one of claims 1 to 6.

8. A laminate comprising two or more layers made of the cured material of claim 7, wherein any layer made of the cured material comprises a metal layer between each other.

9. A semiconductor device comprising the cured material of claim 7.

10. A method for manufacturing a cured material, comprising: In the film forming process, a film is formed on a substrate by applying a resin composition containing a precursor of a cyclized resin. The exposure process involves selectively exposing the film. In the developing process, a developing solution is used to develop the film to form a pattern; and The heating process involves heating the pattern at a temperature above 50°C and below 250°C. The precursor of the cyclized resin is a compound that produces an alkali during the heating process. The precursor of the cyclized resin comprises at least one repeating unit selected from the following formula (2), repeating unit represented by formula (3), and repeating unit represented by formula (PAI-2). 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 independently represent a hydrogen atom or a monovalent organic group, R 111 R 115 R 113 and R 114 At least one of them contains a structure represented by the following equation (1-1), In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can independently represent a hydrogen atom or a monovalent organic group, R 121 R 122 R 123 and R 124 At least one of them contains a structure represented by the following equation (1-1), In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 R represents a hydrogen atom or a monovalent organic group. 117 R 111 and R 113 At least one of them contains a structure represented by the following equation (1-1), In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 Optional connections form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

11. The method for manufacturing a cured product according to claim 10, wherein, Regarding the film after the exposure process and before the development process, the ratio F / E of the number of moles of alkali-generating groups present in the film as the pattern residue before the development process to the number of moles of alkali-generating groups present in the pattern after the development process exceeds 0.

9.

12. The method for manufacturing a cured product according to claim 10 or 11, wherein, In the membrane formed during the membrane forming process, the ratio of the concentration X of alkali-generating groups in the upper 50% of the membrane thickness direction to the concentration Y of alkali-generating groups in the lower 50% is 0.90 < X / Y < 1.

10.

13. The method for manufacturing a cured product according to claim 10 or 11, wherein... The ratio of the closed-loop ratio A on the opposite side of the cured product to the closed-loop ratio B on the side of the cured product in contact with the substrate, A / B, is 0.90 < A / B < 1.

10.

14. The method for manufacturing a cured product according to claim 10 or 11, wherein, When a 1:1 line and space pattern with a film thickness of 20 μm and a spacing of 10 μm is formed in the developing process, and the pattern is heated at 230°C for 180 minutes in the heating process, the ratio of the width shrinkage rate C at the upper end of the line pattern to the width shrinkage rate D at the lower end, C / D, is 0.90 < C / D < 1.

10.

15. A precursor of a cyclized resin, comprising at least one repeating unit selected from repeating units represented by formula (2), repeating units represented by formula (3), and repeating units represented by formula (PAI-2). 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 independently represent a hydrogen atom or a monovalent organic group, R 111 R 115 R 113 and R 114 At least one of them contains a structure represented by the following equation (1-1), In equation (3), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can independently represent a hydrogen atom or a monovalent organic group, R 121 R 122 R 123 and R 124 At least one of them contains a structure represented by the following equation (1-1), In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 R represents a hydrogen atom or a monovalent organic group. 117 R 111 and R 113 At least one of them contains a structure represented by the following equation (1-1), In equation (1-1), R 1 Each is independently a hydrogen atom or a monovalent organic group, with two R atoms. 1 Optional connections form a ring structure, L 1 * indicates a trivalent organic group, and * indicates a bonding site with other structures.

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