Methods for manufacturing hardened materials, methods for manufacturing multilayers, methods for manufacturing semiconductor devices, and processing solutions and resin compositions.

Abstract

This invention provides a method for manufacturing a cured material that yields a cured material with excellent elongation at break, a method for manufacturing a laminate including the above-described method for manufacturing a cured material, and a method for manufacturing a semiconductor device including the above-described method for manufacturing a cured material or the above-described method for manufacturing a laminate. It also provides a processing liquid and a resin composition used in the above-described method for manufacturing a cured material. The method for manufacturing a cured material includes: a film forming step, in which a resin composition comprising a precursor of a cyclized resin and a polymerizable compound having urea bonds is applied to a substrate to form a film; a processing step, in which a processing liquid is brought into contact with the film; and a heating step, in which the film is heated after the processing step, wherein the processing liquid comprises at least one compound selected from the group consisting of basic compounds and alkali-generating agents.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a hardened material, a method for manufacturing a multilayer, a method for manufacturing a semiconductor device, and a processing liquid and resin composition. Prior Technology

[0002] Resins such as polyimide possess excellent heat resistance and insulation properties, making them suitable for a wide range of applications. While there are no particular limitations on these applications, examples include the use of patterns containing these resins as insulating films, sealing materials, or protective films in the context of actual semiconductor device mounting. Furthermore, patterns containing these resins can also be used as base films or 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 containing precursors of cyclized resins such as polyimide precursors. The resin composition is applied to a substrate by means of coating, and then exposed, developed, heated, etc., as needed, thereby forming a hardened product containing cyclized resin (e.g., a resin in which polyimide precursors are amide-modified) on the substrate. Resin compositions can be applied using known coating methods, and can be developed to form fine patterns and complex shapes. Therefore, it can be said that the cured products offer a high degree of design freedom and excellent manufacturing adaptability. Considering this excellent manufacturing adaptability in addition to the high performance of polyimide, there is growing anticipation for the industrial application development of manufacturing methods for cured products using resin compositions containing polyimide precursors.

[0004] For example, Patent Document 1 describes a pattern forming method characterized by exposing a photosensitive polyimide layer on a substrate to photocuring it into a suitable pattern, followed by developing it to remove unexposed portions, immersing the substrate with the photocured polyimide pattern layer in a rinsing solution containing at least 5-30% by volume of a primary aliphatic amine compound and 2-20% by volume of an aprotic alkaline solvent to rinse the substrate, and finally heat-treating the substrate with the photocured polyimide layer removed from the rinsing solution at high temperature. Patent Document 2 describes a pattern forming method, characterized in that, in the method of forming a predetermined pattern from a photosensitive composition containing a photocrosslinkable polymer having specific repeating units, when developing by spraying or immersion developing using an automatic machine, two or more developing solutions with different solubilities relative to the aforementioned photocrosslinkable polymer are used in order of their highest solubility.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 1-221741 [Patent Document 2] Japanese Patent Application Publication No. 7-209879 Summary of the Invention

[0006] Traditionally, a resin composition containing a cyclized resin precursor such as a polyimide precursor has been applied to a substrate to form a film, which is then cured by heating the precursor as a cyclized resin. This cyclization process improves the mechanical properties of the film (e.g., elongation at break) and enhances the reliability of modules incorporating the film. In the past, attempts have been made to improve the elongation at break of the film by promoting the cyclization of the cyclized resin, but there is still room for improvement in terms of elongation at break.

[0007] The present invention aims to provide a method for manufacturing a hardened material that can obtain a hardened material with excellent elongation at break, a method for manufacturing a laminate including the above-mentioned method for manufacturing a hardened material, and a method for manufacturing a semiconductor device including the above-mentioned method for manufacturing a hardened material or the above-mentioned method for manufacturing a laminate, and to provide a processing liquid and resin composition used in the above-mentioned method for manufacturing a hardened material.

[0008] Examples of representative embodiments of the present invention are shown below. <1> A method for manufacturing a hardened material, comprising: The film formation step involves applying a resin composition comprising a cyclized resin precursor and a polymerizable compound having urea bonds onto a substrate to form a film. The processing steps involve contacting the processing solution with the aforementioned membrane; and The heating step involves heating the membrane after the above processing steps. The above-mentioned treatment solution contains at least one compound selected from the group consisting of alkaline compounds and alkali-generating agents. <2> like <1> The method for manufacturing the hardened material includes, between the film formation step and the processing step, an exposure step of selectively exposing the film and a development step of developing the exposed film with a developer to form a patterned film. <3> like <1> or <2> In the method for manufacturing the hardened material, the aforementioned processing liquid is a rinsing liquid. <4> like <1> to <3> The method for manufacturing the hardened material according to any one of the above methods, wherein the above processing step is a rinsing step of cleaning the above membrane with the above processing solution. <5> like <1> to <4> The method for manufacturing a hardened material according to any one of the above methods includes, between the above film formation step and the above processing step, an exposure step for selectively exposing the film, wherein the processing step is a step of developing the film by using the above processing solution as a developing solution to form a patterned film. <6> like <5> The method for manufacturing the hardened material further includes, after the above-mentioned processing steps, a second processing step of contacting a second processing liquid with the patterned membrane, wherein the second processing liquid contains at least one compound selected from the group consisting of alkaline compounds and alkali generating agents. <7> like <2> to <6> The method for manufacturing a hardened material according to any one of the claims, wherein the development described above is negative development. <8> like <1> to <7> The method for manufacturing the hardened material according to any one of the claims, wherein the polymeric compound having a urea bond comprises a monofunctional polymeric compound having only one polymeric group. <9> like <1> to <8> A method for manufacturing the hardened material according to any one of the claims, wherein the resin composition further comprises a polymerization initiator. <10> like <1> to <9> The method for manufacturing the hardened material according to any one of the claims, wherein the alkaline compound is an amine and the alkali generating agent is a compound that generates amine. <11> like <1> to <10> The method for manufacturing the hardened material according to any one of the claims, wherein the alkaline compound is a secondary or tertiary amine, and the alkali generating agent is a compound that generates a secondary or tertiary amine. <12> like <1> to <11> The method for manufacturing the hardened material according to any one of the claims, wherein the alkaline compound is an alkaline compound having an amino group, and the alkali generating agent is an alkali generating agent having an amino group. <13> like <1> to <12> A method for manufacturing the hardened material according to any one of the above-mentioned methods, wherein the alkaline compound and the alkaline generating agent have acrylamide or methacrylamide groups. <14> like <1> to <13> The method for manufacturing the hardened material according to any one of the claims, wherein the treatment liquid further contains a polymerization inhibitor. <15> like <1> to <14> The method for manufacturing the hardened material according to any one of the above methods, wherein the material contains 50% by mass or more of an organic solvent relative to the total mass of the above-mentioned treatment liquid. <16> like <1> to <15> The method for manufacturing the hardened material according to any one of the claims, wherein the precursor of the cyclized resin is a polyimide precursor. <17> like <1> to <16> The method for manufacturing the hardened material according to any one of the claims, wherein the heating step is a step of promoting the cyclization of the precursor of the cyclized resin by heating using the action of at least one alkaline compound selected from the group including the alkaline compound and alkaline compounds generated from the alkaline generating agent. <18> like <1> to <17> The method for manufacturing the hardened material according to any one of the above-mentioned heating steps, wherein the heating temperature in the heating step is 120~230°C. <19> A method for manufacturing a laminate, comprising a plurality of steps <1> to <18> The method for manufacturing the hardened material as described in any one of the above. <20> like <19> The method for manufacturing the laminated body further includes a metal layer forming step of forming a metal layer on the hardened material between the plurality of times the above-described method for manufacturing the hardened material. <21> A method for manufacturing a semiconductor device, comprising: <1> to <18> The method for manufacturing the hardened material as described in any one of the above methods or <19> or <20> The method for manufacturing the laminated body. <22> A processing liquid used in a method for manufacturing a cured product, the method comprising: a film forming step of applying a resin composition comprising a precursor of a cyclized resin and a polymeric compound having urea bonds onto a substrate to form a film; a processing step of contacting the processing liquid with the film; and a heating step of heating the film after the processing step, wherein... The treatment solution contains at least one compound selected from the group consisting of basic compounds and alkali-generating agents. <23> like <22> The processing solution, wherein the method for manufacturing the hardened material further includes an exposure step of selectively exposing the film formed by the film forming step and a developing step of developing the exposed film with a developing solution to form a patterned film, wherein the processing step is a rinsing step of cleaning the patterned film with the processing solution. <24> A resin composition comprising a precursor of a cyclized resin is provided in a method for manufacturing a cured article, the method comprising: a film forming step of applying the resin composition onto a substrate to form a film; a processing step of contacting the film with a processing liquid; and a heating step of heating the film after the processing step. <25> like <24> The resin composition further comprises a polymeric compound having urea bonds. [Invention Effects]

[0009] According to the present invention, a method for manufacturing a hardened material that can obtain a hardened material with excellent elongation at break is provided, a method for manufacturing a laminate including the above-mentioned method for manufacturing a hardened material, a method for manufacturing a semiconductor device including the above-mentioned method for manufacturing a hardened material or the above-mentioned method for manufacturing a laminate, and a processing liquid and resin composition used in the above-mentioned method for manufacturing a hardened material are provided. Simple Explanation of the Diagram

[0010] Figure 1 is a schematic cross-sectional view of the test vehicle used in the bias HAST test. Implementation

[0011] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” represents the range within which the values ​​recorded before and after “~” are respectively taken as the lower limit and upper limit. In this specification, the term "step" not only refers to an independent step, but also includes steps that cannot be clearly distinguished from other steps, as long as the intended function of the step can be achieved. Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) 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). In this specification, unless otherwise stated, “exposure” includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, 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 photochemical rays or radiation. In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acrylyl” means “acrylyl” and “methacrylyl” or either one. In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. 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 all components other than the solvent relative to the total mass of the composition. In this instruction manual, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel osmosis chromatography (GPC) and are defined as polystyrene equivalents. In this instruction manual, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise stated, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. In cases where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise stated, the detection in GPC assays uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when referring to the positional relationship of the layers constituting the laminate as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the multiple layers of concern. That is, a third layer or element may be sandwiched between the reference layer and the other layers mentioned above, and the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise stated, the direction in which the layers are gradually stacked on the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, this up-down orientation is for the convenience of explaining this instruction manual. In actual practice, the "up" orientation in this instruction manual may also differ from "vertically up". In this specification, unless otherwise stated, each component included in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to that component. In this instruction manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the better state sample is referred to as the superior state sample.

[0012] (Manufacturing method of hardened material) The method for manufacturing the hardened material of the present invention includes: a film forming step, wherein a resin composition comprising a precursor of a cyclized resin and a polymeric compound having urea bonds is applied to a substrate to form a film; a processing step, wherein a processing liquid is brought into contact with the film; and a heating step, wherein the film is heated after the processing step, wherein the processing liquid comprises at least one compound selected from the group consisting of basic compounds and alkali generating agents.

[0013] According to the manufacturing method of the hardened material of the present invention, a hardened material with excellent elongation at break can be obtained. The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0014] In the method for manufacturing the cured material, the following steps are performed: after applying a resin composition containing a cyclized resin precursor such as a polyimide precursor onto a substrate to form a film, the film is heated to obtain the cured material. Among these requirements, the hardened material must possess excellent mechanical strength (high elongation at break). In the method for manufacturing the cured product of the present invention, the resin composition comprises a polymeric compound having urea bonds, and the method for manufacturing the cured product includes a step of contacting the film with a treatment liquid before the heating step (contact step), and the treatment liquid comprises at least one compound selected from the group consisting of alkaline compounds and alkali generating agents. It is believed that by including polymeric compounds with urea bonds in the resin composition, alkaline compounds or alkali-generating agents can easily penetrate into the membrane. Subsequently, it was found that when the aforementioned membrane is heated, the cyclization of the cyclizing resin precursor is promoted by the action of at least one of the aforementioned alkaline compound and the alkaline compound generated from the aforementioned alkaline generating agent. As a result, it was found that a cured product with a high elongation at break can be obtained according to the method for manufacturing the cured product according to the present invention.

[0015] Furthermore, in recent years, the size of substrates has increased from 8-inch wafers to 12-inch wafers and panel sizes. Also, in order to install copper wiring and other wiring, the number of layers required has gradually increased from 1 layer to 2, 3, 4, and 5 layers. Due to the large area of ​​the substrate (base material) and the increase in the number of layers to be stacked during this type of manufacturing, the warping of the wafer or panel is significant. Therefore, it is desirable to perform the heating in the above heating steps at a low temperature. Furthermore, in order to suppress thermal damage to other materials in the component, accelerate the manufacturing process, and achieve energy saving, it is desirable to perform the heating in the above heating steps at a low temperature. According to the method for manufacturing the cured product of the present invention, it is believed that even when the heating step is performed at a low temperature (e.g., below 230°C, further below 200°C, below 180°C, etc.), a cured product with a high elongation at break due to the promotion of cyclization of the aforementioned cyclized resin precursor can be obtained. Therefore, the method for manufacturing the cured product of the present invention is considered useful even when heating at such a low temperature is required.

[0016] In Patent Documents 1 and 2, the method for manufacturing the cured material is not described. The method for manufacturing the cured material includes: a film forming step, in which a resin composition comprising a precursor of a cyclized resin and a polymeric compound having urea bonds is applied to a substrate to form a film; and a treatment step, in which a treatment liquid is brought into contact with the film, wherein the treatment liquid comprises at least one compound selected from the group consisting of alkaline compounds and alkali generating agents. The method for manufacturing the hardened material of the present invention will be described in detail below.

[0017] <Membrane Formation Steps> The method for manufacturing the cured material of the present invention includes a film forming step of applying a resin composition comprising a precursor of a cyclized resin and a polymeric compound having urea bonds onto a substrate to form a film. The details of the resin composition used in this invention will be described later.

[0018] [Substrate] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates with metal layers formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, the surface of such substrates may have a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS). Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. For the dimensions of the substrate, if it is circular, the diameter is, for example, 100~450mm, preferably 200~450mm. If it is rectangular, the length of the shorter side is, for example, 100~1000mm, preferably 200~700mm. Furthermore, as a substrate, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0019] Furthermore, in cases where a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed from a hardened material) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0020] Coating is a preferred method for applying resin compositions to a substrate.

[0021] Methods for applying resin compositions to substrates include, specifically, 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 preferred. From the viewpoints of film thickness uniformity and productivity, spin coating and slot coating are better. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method of applying the resin composition to the substrate, a film of the desired thickness can be obtained. Furthermore, the method of applying the resin composition to the substrate (coating method) can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, the method of applying the resin composition to the substrate can also be applied to the method of transferring a coating pre-formed on the dummy support by the method described above onto the substrate (transfer method). 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 can also be preferred in this invention. Furthermore, a step can be performed to remove excess film from the ends of the substrate. Examples of such steps include edge bead rinsing (EBR) and back rinse. Alternatively, a pre-wetting step can be used, in which various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate.

[0022] <Drying Steps> After the film formation step (layer formation step), the above-mentioned film can be used in the drying step (drying step) to remove the solvent. That is, the method for manufacturing the hardened material of the present invention may include a drying step, which dries the film formed by the film forming step. Furthermore, it is preferable that the drying step described above is performed after the film formation step and before the processing step. Moreover, if the method for manufacturing the cured material includes the exposure step described later, it is preferable that the drying step is performed before the exposure step. The preferred drying temperature for the membrane during the drying process is 50~150℃, more preferably 70℃~130℃, and even more preferably 90℃~110℃. Alternatively, drying can be performed under reduced pressure. For drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are even better.

[0023] <Processing Steps> The method for manufacturing the hardened material of the present invention includes a processing step in which a processing solution is brought into contact with the aforementioned membrane.

[0024] [Treatment solution] The treatment solution used in the treatment steps contains at least one compound selected from the group consisting of alkaline compounds and alkali-generating agents.

[0025] It is preferable that the treatment solution contains at least one compound selected from the group consisting of basic compounds having amide groups and alkali-generating agents having amide groups. That is, it is preferable that the above-mentioned alkaline compound is an alkaline compound with an amino group and the above-mentioned alkali generating agent is an alkali generating agent with an amino group. From the viewpoint of reducing residues in the hardened material, it is preferable that the treatment liquid of the present invention contains an alkaline compound having a amide group, and it is even more preferable that it contains an alkaline compound having a low boiling point amide group.

[0026] In this invention, the amide group refers to the group represented by *-NR NC(=O)-*, and the amide group or a portion thereof can form a ring structure. RN represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. The asterisks above all indicate the bonding sites with carbon atoms. The number of amide groups in the above-mentioned basic compounds containing amide groups is not particularly limited, but 1 to 10 is preferred, 1 to 4 is even more preferred, 1 or 2 is further preferred, and 1 is particularly preferred. The number of amide groups in the above-mentioned alkali-generating agents with amide groups is not particularly limited, but 1 to 10 is preferred, 1 to 4 is even better, 1 or 2 is further preferred, and 1 is especially preferred.

[0027] The above-mentioned basic compounds containing amide groups preferably include acrylamide or methacrylamide groups as structures containing the aforementioned amide groups. The aforementioned alkali-generating agent containing an acrylamide group is preferably composed of an acrylamide group or a methacrylamide group. In the case where the above-mentioned alkali generating agent containing an acrylamide group includes an acrylamide group or a methacrylamide group as a structure containing the above-mentioned acrylamide group, the acrylamide group or the methacrylamide group can be present in the structure that becomes the alkaline compound to be generated, or it can be present in the structure that becomes the residue after the alkaline compound is generated, but it is preferable that it is present in the structure that becomes the alkaline compound to be generated. It is believed that by containing an alkaline compound containing acrylamide or methacrylamide in the treatment liquid, or an alkaline generating agent containing acrylamide or methacrylamide, during the heating step, a chemical reaction such as polymerization occurs between the aforementioned acrylamide or methacrylamide and the polymerizable groups in the resin or polymerizable compound, and the degassing amount of the treatment liquid may sometimes be reduced.

[0028] Furthermore, from the viewpoint of the preservation stability of the resin composition and the elongation at break of the obtained cured product, the above-mentioned basic compound is preferably an amine, and secondary or tertiary amines are even better. From the viewpoint of the elongation at break of the obtained hardened material, it is preferable that the above-mentioned alkali generating agent is a compound that generates amines, and even better that it generates secondary or tertiary amines. Among them, amines refer to compounds in which the hydrogen atoms of ammonia are replaced by hydrocarbon groups or aromatic groups. If one hydrogen atom is replaced, it is a primary amine; if two hydrogen atoms are replaced, it is a secondary amine; and if three hydrogen atoms are replaced, it is a tertiary amine, and so on.

[0029] When the basic compound is an amine (the basic compound having an amino group is a primary amine, secondary amine, or tertiary amine, and also has an amino group), the number of amino groups in the basic compound is not particularly limited, but 1 to 10 is preferred, 1 to 4 is more preferred, 1 or 2 is further preferred, and 1 is especially preferred. Furthermore, when the basic compound generated from the above-mentioned alkali generating agent is an amine, the number of amine groups in the basic compound is not particularly limited, but 1 to 10 is preferred, 1 to 4 is even more preferred, 1 or 2 is further preferred, and 1 is particularly preferred.

[0030] -Alkaline compounds containing amino groups- The basic compound with a amide group used in this invention is preferably a compound with the structure represented by the following formula (1-1). [Chemical Formula 1] In formula (1-1), R1 and R2 independently represent hydrogen atoms or monovalent organic groups, R1 and R2 can be bonded to form a ring structure, L1 represents a divalent linker, and at least one of L1, R1 and R2 can be bonded to form a ring structure, RN represents hydrogen atoms or monovalent organic groups, and R3 represents a monovalent organic group.

[0031] In formula (1-1), it is preferable that R1 and R2 are independently hydrogen atoms or hydrocarbon groups, and even more preferable that they are hydrogen atoms or alkyl groups. It is preferred that the hydrocarbon group or alkyl group in R1 and R2 has 1 to 20 carbons, 1 to 10 is more preferred, and 1 to 4 is even more preferred. Furthermore, in this specification, when simply referred to as hydrocarbon group, alkyl group, alkyl group, etc., it also includes any of the structures represented by straight chain, branched chain, cyclic, or such bonds. In formula (1-1), it is preferable that at least one of R1 and R2 is a monovalent organogroup, and it is even more preferable that both are monovalent organogroups. R1 and R2 can bond together to form a ring structure. The formed ring structure can be an aromatic ring structure or an aliphatic ring structure. Furthermore, a 5-membered or 6-membered ring structure is preferred. Furthermore, in equation (1-1), it is also possible to use a state in which R1 and R2 are not bonded and do not form a ring structure.

[0032] In formula (1-1), L1 is preferably a hydrocarbon group or a group represented by a hydrocarbon group bonded to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -SO2-, and -NR-, with a hydrocarbon group being more preferred. R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom or a hydrocarbon group being more preferred, a hydrogen atom or an alkyl group being more preferred, and a hydrogen atom being even more preferred. Preferably, the bonding sites between L1 and the two nitrogen atoms are both hydrocarbon groups. As for the hydrocarbon group in L1, alkyl groups are preferred. For the number of carbon atoms in the hydrocarbon group of L1, 1 to 20 is preferred, 1 to 10 is even better, and 1 to 4 is further preferred. At least one of L1, R1, and R2 can be bonded to form a ring structure. The formed ring structure can be an aromatic ring structure or an aliphatic ring structure. Furthermore, a 5-membered or 6-membered ring structure is preferred. Furthermore, in equation (1-1), any one of L1, R1, and R2 can be used without forming a ring structure.

[0033] In formula (1-1), RN represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0034] In formula (1-1), R 3 represents a monovalent organic group, preferably a hydrocarbon group, and more preferably an alkyl or alkenyl group. It is preferred that the number of carbon atoms in the above-mentioned alkyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4. In particular, R3 being a vinyl or 2-methyl vinyl form is also one of the preferred forms of the present invention.

[0035] Furthermore, basic compounds with amide groups can be polymers. Regarding polymers that are basic compounds containing amide groups, examples include polymers possessing repeating units having both amide and amino groups. It is preferable that the aforementioned amino groups are secondary or tertiary amino groups. As a polymer, examples include polymers containing repeating units represented by the following formulas (1-2). [Chemical Formula 2] In equation (1-2), R1 and R2 independently represent hydrogen atoms or monovalent organic groups, R1 and R2 can be bonded to form a ring structure, L1 represents a divalent linker, and at least one of L1, R1 and R2 can be bonded to form a ring structure, RN represents hydrogen atoms or monovalent organic groups, and R4 represents hydrogen atoms or monovalent organic groups. In equation (1-2), R1, R2, RN and L1 have the same meaning as R1, R2, RN and L1 in equation (1-1), and the better state is also the same. In formula (1-2), it is preferable for R4 to be a hydrogen atom or an alkyl group, and even more preferable for it to be a hydrogen atom or a methyl group.

[0036] <<Physical Properties>> When the basic compound containing the amide group is a low molecular weight compound, there is no particular limitation on the molecular weight of the basic compound containing the amide group, but it is preferable to be as small as possible. For example, 500 or less is preferred, and 200 or less is even more preferred. There is no particular limitation on the lower limit value, but 45 can be cited as an example. Furthermore, when the basic compound having an amino group is a polymer, it is preferable that the weight average molecular weight of the polymer is as small as possible, for example, 2,000 or less.

[0037] There is no particular limitation on the boiling point of basic compounds with amide groups at 1 atmosphere, but below 200°C is preferred, below 180°C is even better, and below 160°C is further preferred. Furthermore, hereafter, "1 atmosphere" is sometimes also marked as "atmospheric pressure" or "atmospheric pressure (101,325 Pa)," but they have the same meaning. There is no particular limitation on the melting point of basic compounds with amino groups at 1 atmosphere, but it is better if they are liquid at room temperature (23°C). Furthermore, when the treatment solution contains a solvent, it is preferable that the boiling point of the basic compound having an amino group at 1 atmosphere is a temperature obtained by subtracting 20°C from the boiling point of the solvent contained in the treatment solution at 1 atmosphere, and even more preferably, the boiling point of the solvent contained in the treatment solution at 1 atmosphere is also preferable. For example, if the boiling point of the solvent at 1 atmosphere is 100°C, it is preferable that the boiling point of the basic compound having an amino group at 1 atmosphere is 80°C or higher, and even more preferably, the boiling point at 1 atmosphere is 100°C or higher. There is no particular limitation on the pKa of conjugate acids of basic compounds containing amide groups, but 0 or higher is preferred, 3 or higher is even more preferred, and 6 or higher is even more preferred. There is no particular limitation on the upper limit of the pKa of the above-mentioned conjugate acids, but 30 or lower is preferred. pKa is the negative common logarithm of the equilibrium constant Ka, which takes into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise stated, pKa is assumed to be a value calculated based on ACD / ChemSketch (registered trademark). In the case of multiple pKas of the above-mentioned conjugate acids, it is preferable that at least one is within the above-mentioned range.

[0038] <<Specific examples>> Examples of basic compounds having a amide group include the following compounds, but the list is not limited to them. [Chemical Formula 3]

[0039] <<Content>> The content of alkaline compounds relative to the total mass of the treatment solution is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. Furthermore, there is no particular limitation on the lower limit of the above content, but 0.1% by mass or more is preferred. Furthermore, the content of alkaline compounds relative to the total mass of the treatment solution is preferably 70-100% by mass. The treatment solution may contain only one type of alkaline compound, or it may contain two or more types. When there are two or more alkaline compounds, it is preferable that their total content falls within the range described above.

[0040] -Other basic compounds- The treatment solution may contain an alkaline compound (also referred to as "other alkaline compounds") that does not have an amino group. From the viewpoint of reliability when remaining on the hardened film (adhesion to the substrate when the hardened material is further heated), organic bases are preferred as other alkaline compounds. Furthermore, as other basic compounds, basic compounds with an amino group are preferred, such as primary amines, secondary amines, tertiary amines, and ammonium salts. However, in order to promote the aceimide reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are even better, secondary amines or tertiary amines are further preferred, and tertiary amines are especially preferred. As for other basic compounds, from the viewpoint of the mechanical properties (elongation at break) of the hardened material, it is better if they are less likely to remain in the hardened film (the obtained hardened material), and from the viewpoint of promoting aceiminization, it is better if the amount of residue is not easily reduced due to vaporization before heating. Therefore, the boiling points of other basic compounds are preferably 30°C to 350°C at normal pressure (101,325 Pa), even better at 80°C to 270°C, and further better at 100°C to 230°C. Furthermore, it is preferable that the boiling point of other alkaline compounds is above the temperature obtained by subtracting 20°C from the boiling point of the solvent contained in the treatment solution, and even more preferably above the boiling point of the solvent contained in the treatment solution. For example, when the boiling point of the organic solvent is 100°C, it is preferable that the boiling point of the alkaline compound used is above 80°C, and even more preferable that it is above 100°C.

[0041] Specific examples of other basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyl... Dicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinylamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine. The treatment solution may contain only one other alkaline compound, or it may contain two or more.

[0042] -Base-producing agents with amino groups- As an alkali-generating agent with amide groups used in this invention, it is possible to use alkali-generating agents with amide groups used in the resin composition of this invention described later without particular limitation. Furthermore, alkali-generating agents with amino groups can be either photoalkali-generating agents or thermal alkali-generating agents, but thermal alkali-generating agents are preferred.

[0043] <<Physical Properties>> The preferred state of the base produced from the base-generating agent with amide groups has the same molecular weight, boiling point, melting point, pKa, and other physical properties as the preferred state of the bases with amide groups mentioned above.

[0044] <<Specific examples>> Examples of base-generating agents with amide groups include, but are not limited to, the following compounds. [Chemical Formula 4]

[0045] -Other alkali-generating agents- The treatment solution may contain an alkali-generating agent (also referred to as "other alkali-generating agents") that does not have amide groups as the aforementioned alkali-generating agent. As other alkali-generating agents, those that do not have amide groups and are used in the resin composition of the present invention described later can be used without particular limitation. Furthermore, other alkali generating agents can be light-induced alkali generating agents or heat-induced alkali generating agents, but heat-induced alkali generating agents are preferred.

[0046] <<Content>> The content of the alkali generating agent relative to the total mass of the treated liquid is preferably 10% by mass or less, and more preferably 5% by mass or less. Furthermore, the content is preferably 0.1% by mass or more. The treatment solution may contain only one type of alkali-generating agent, or it may contain two or more types. When there are two or more alkali-generating agents, it is preferable that their total content falls within the range mentioned above.

[0047] -Polymerization Inhibitor- It is preferable that the treatment solution further contains polymerization inhibitors. The processing liquid of the present invention comprises at least one compound selected from the group consisting of an alkaline compound having an acrylamide group or a methacrylamide group and an alkaline generating agent having an acrylamide group or a methacrylamide group, and the embodiment containing a polymerization inhibitor is also one of the preferred embodiments of the present invention. There are no particular limitations on what constitutes a polymerization inhibitor, but examples include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0048] Specific compounds used as polymerization inhibitors include, preferably, p-hydroquinone, o-hydroquinone, 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 -Nitrosino-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(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, phenthiazolinone, phenanthrene, 1,1-diphenyl-2-pyrrolidine, dibutyldithiocopper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, 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 can also be used, and such contents are incorporated into this specification.

[0049] When the treatment solution contains polymerization inhibitors, the content of polymerization inhibitors relative to the total solids content of the treatment solution is preferably 0.01~20% by mass, more preferably 0.01~15% by mass, further preferably 0.01~10% by mass, even more preferably 0.02~15% by mass, and particularly preferably 0.05~10% by mass. There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that the total number is within the above range.

[0050] -solvent- The treatment solution may contain a solvent. Examples of solvents include water or organic solvents, with organic solvents being preferred. Examples of organic solvents, and of the form of esters, preferably include 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-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, alkyl 3-alkoxypropionic acid). Ethyl hydroxypropionate, 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., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate) ethyl 2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, Examples of preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and anisole; cyclic terpenes such as limonene; dimethyl sulfoxide as a sulfide; methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol as alcohols; and N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylmethamide as acetamides. Furthermore, when the alkaline compound (e.g., the alkaline compound having an amino group or other alkaline compound) is in liquid form when using a processing liquid, such alkaline compound can be used as both a solvent and an alkaline compound.

[0051] When the treatment solution contains a solvent, it is preferable that the solvent content is 50% by mass or more relative to the total mass of the treatment solution, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Furthermore, when the treatment solution contains organic solvents, it is preferable that the content of organic solvents is 50% by mass or more relative to the total mass of the treatment solution, more preferably 70% by mass or more, and even more preferably 90% by mass or more. There may be only one solvent or two or more solvents. When there are two or more solvents, it is preferable that their total number is within the above range. When the processing solution contains two or more solvents, it is preferable that the solvents include at least two selected from the group consisting of ether-based solvents and ester-based solvents. Examples of such solvents include those containing PGMEA and γ-butyrolactone, and those containing butyl acetate and γ-butyrolactone.

[0052] -Other ingredients- The treatment solution may further contain other components. Other components include, for example, well-known surfactants and well-known defoamers.

[0053] Between the above-described film formation step and the above-described processing step, it is preferable to include an exposure step that selectively exposes the film and a development step that develops the exposed film with a developer to form a patterned film. Hereinafter, the state sample in which the film formation step, exposure step, development step and processing step are performed is also described as state sample A. In sample A, the above processing steps are steps that bring the patterned film obtained by the development step into contact with the processing solution.

[0054] [Method for supplying the treatment fluid] Regarding the method of supplying the processing solution, there are no particular limitations as long as the processing solution can come into contact with the membrane. However, examples include supplying the processing solution to the membrane obtained in the membrane formation step, supplying the processing solution to the exposed membrane after the exposure step described later, and supplying the processing solution to the patterned membrane. There are no particular limitations on the above-mentioned supply methods. There are methods such as immersing the substrate in the treatment liquid, supplying the substrate based on swirling immersion (liquid tray), supplying the treatment liquid to the substrate in the form of spraying, and continuously supplying the treatment liquid to the substrate by means of a mechanism such as a straight nozzle. From the perspectives of the permeability of the processing liquid to the image area, the removal of the non-image area, and manufacturing efficiency, there are methods for supplying the processing liquid using spray nozzles, straight nozzles, spray nozzles, etc. The method of continuous supply using nozzles is better. From the perspective of the permeability of the processing liquid to the image area, the method of using nozzles to retain the processing liquid on the substrate is better. The above-mentioned methods for supplying the processing fluid can be used simultaneously (e.g., a combination of supply based on swirling immersion and supply based on spraying, or a combination of supply based on swirling immersion and supply based on a straight nozzle). For example, swirling immersion supply has the effect of making the processing fluid easier to penetrate after the film expands, while spraying or misting supply can improve the removal of non-image areas. Furthermore, the processing fluid only needs to be used in at least one of the methods used simultaneously. In this invention, the following configuration can be established: after supplying a liquid containing either an alkaline compound having a amide group or an alkali-generating agent having a amide group to the pattern (for example, after supplying a rinsing solution containing either an alkaline compound having a amide group or an alkali-generating agent having a amide group to the patterned membrane to clean the pattern), a treatment step based on the treatment solution is performed. The method of supplying the treatment liquid containing either an alkaline compound having a amide group or an alkali generating agent having a amide group to the pattern is not particularly limited, but a method based on tumble soaking can be cited. There are no particular limitations on the method of supplying the processing liquid to the pattern as described above, but preferred examples include supply based on spraying and supply based on a straight nozzle. It is believed that by immersing the pattern in a treatment solution that does not contain either an alkaline compound with an amino group or an alkali-generating agent with an amino group, the pattern expands. Afterward, at least one compound selected from the group consisting of alkaline compounds with amino groups and alkali-generating agents with amino groups is supplied in the treatment solution, allowing it to easily penetrate the pattern and more readily achieve effects such as increased elongation at break. Furthermore, supplying the treatment solution via spraying, a straight nozzle, or similar means sometimes results in excellent removal (rinsing) of developing residues. Furthermore, as a method for supplying the treatment liquid in the processing step, steps such as continuously supplying the treatment liquid to the substrate, keeping the treatment liquid in a substantially static state on the substrate, vibrating the treatment liquid on the substrate using ultrasound or the like, and combinations thereof can be adopted. Among these, the step of supplying or continuously supplying the processing liquid to the developed pattern by means of diffusion radiation such as spraying or sprinkling is preferred. Furthermore, it is preferable that the development step is performed by immersion development, and that at least one supply of the processing solution in the processing step is performed by continuous supply based on spraying or by a straight nozzle. Based on the above, it is believed that by immersion development, the pattern expands, making it easier for at least one compound selected from the group including alkaline compounds and alkali-generating agents in the processing solution to penetrate into the pattern, thereby making it easier to obtain effects such as improved elongation at break.

[0055] The processing time (i.e., the time the processing solution contacts the pattern) in the processing step is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular requirement for the temperature of the processing solution during the processing step, but it is preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

[0056] <<Exposure Steps>> The method for manufacturing the hardened material of the present invention may include an exposure step, which selectively exposes the film formed by the film forming step. Selective exposure means exposing a portion of the film. Furthermore, through selective exposure, exposed areas (exposed portions) and unexposed areas (unexposed portions) are formed on the film. Regarding the exposure amount, there are no special requirements as long as it can harden the resin composition. For example, an exposure energy of 50~10,000mJ / cm2 at a wavelength of 365nm is preferred, and 200~8,000mJ / cm2 is even better.

[0057] The exposure wavelength can be appropriately set within the range of 190~1,000nm, with 240~550nm being the optimal range.

[0058] Regarding the exposure wavelength, if we explain it in relation to the light source, we can cite (1) semiconductor lasers (wavelengths 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), and wide (three wavelengths of g, 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, etc. Regarding the resin composition, an exposure procedure using a light source containing i-rays at the exposure wavelength is preferred. Examples include high-pressure mercury lamps and wide-angle lamps, but exposure using high-pressure mercury lamps is particularly preferred, especially exposure using i-rays. This allows for particularly high exposure sensitivity. Furthermore, there are no particular limitations on the exposure method, as long as it exposes at least a portion of the film formed by the resin composition. However, examples include exposure using a photomask and exposure based on direct laser imaging.

[0059] <Post-exposure heating steps> The above-mentioned film can be used in the step of heating after exposure (post-exposure heating step). That is, the method for manufacturing the hardened material of the present invention may include a post-exposure heating step, which heats the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50℃~140℃, and even better is 60℃~120℃. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and even better if it is 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, a rate of 1~12℃ / min from the initial heating temperature to the maximum heating temperature is preferred, 2~10℃ / min is even better, and 3~10℃ / min is even more preferred. Furthermore, the heating rate can be adjusted appropriately during the heating process. There are no particular limitations on the heating mechanism used in the post-exposure heating step; commonly known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is also better to conduct the process in a low-oxygen environment by allowing inactive gases such as nitrogen, helium, and argon to flow through during heating.

[0060] <<Developing Steps>> The method for manufacturing the hardened material of the present invention may include a developing step, wherein the developing step uses a developing solution to develop a film exposed by an exposure step to form a patterned film. The exposed and unexposed portions of the film are removed by developing, forming a patterned film. The development process that removes the non-exposed portions of the film through the development step is called negative development, while the development process that removes the exposed portions of the film through the development step is called positive development. In this invention, it is preferable that the development step is negative development.

[0061] [Developing solution] In this invention, the developing solution is a liquid used to form an image by removing unexposed or exposed portions. Developers used in the developing step include those containing organic solvents.

[0062] Regarding developing solutions, preferred examples of esters include 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-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, 3-alkoxy...). Ethyl propionate, 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., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Ethyl 2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example... Examples of preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and anisole; cyclic terpenes such as limonene; dimethyl sulfoxide as a sulfide; methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol as alcohols; and N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylmethamide as acetamides. Furthermore, as described below, the developer contains an alkaline compound. When the alkaline compound (e.g., the aforementioned alkaline compound having an amino group or other alkaline compound) is in liquid form in the environment where the developer is used, such alkaline compound can be used as a solvent and alkaline compound.

[0063] The solvent for the developer can be one or a mixture of two or more. In this invention, it is particularly preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and the developer containing cyclopentanone is the most preferred.

[0064] The solvent content relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can be 100% by mass.

[0065] -Alkaline compounds, alkali-generating agents- In sample A, the developer may contain at least one compound selected from the group consisting of basic compounds and alkali-generating agents. The processing solution used in the above processing steps can be used as the developing solution. Furthermore, in order to suppress pattern expansion caused by alkaline compounds during development, a preferred embodiment of the present invention is a developer solution that does not contain either alkaline compounds or alkali-generating agents. Based on the above embodiment, deviations in pattern shape can sometimes be suppressed. As a preferred example of at least one compound selected from the group including alkaline compounds and alkali generating agents, the alkaline compounds and alkali generating agents contained in the above-mentioned treatment liquid can be cited.

[0066] The developer may further contain other ingredients. Other components include, for example, well-known surfactants and well-known defoamers.

[0067] The developer may further contain other ingredients. Other components include, for example, well-known surfactants and well-known defoamers.

[0068] [Method for supplying developer] Regarding the method of supplying the developer, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate with the film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate for swirling immersion development, or continuously supplying the developer. There are no particular limitations on the type of nozzle, and examples include straight nozzles, spray nozzles, and mist nozzles. For thin films, from the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is better to use a straight nozzle to supply developer or a spray nozzle for continuous supply. From the viewpoint of developer penetration into the image area, the spray nozzle supply method is even better. Alternatively, after continuously supplying developer using a straight nozzle, the substrate can be rotated to remove the developer from the substrate. After rotation drying, the substrate can be continuously supplied again using a straight nozzle, and the substrate can be rotated to remove the developer from the substrate. This process can be repeated several times. Furthermore, as a method for supplying the developer in the developing step, steps such as continuously supplying the developer to the substrate, keeping the developer in a substantially static state on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof can be employed.

[0069] The optimal development time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There are no specific requirements for the temperature of the developing solution during development, but it is best performed at 10 to 45°C, and even better at 18 to 30°C.

[0070] In the processing steps, it is preferable that the above-mentioned treatment solution is a rinsing solution. Rinsing solution is a liquid used to clean the membrane, such as a liquid used to clean patterned membranes after exposure and development. Furthermore, it is preferable that the above-mentioned treatment steps involve rinsing the membrane with the above-mentioned treatment solution. It is preferable that the rinsing step described above is a rinsing step of the patterned film after the exposure and development steps, using the above-mentioned treatment solution. Specifically, by supplying the above-described processing solution to the patterned film after the development step, the processing solution can be used to clean the patterned film.

[0071] Furthermore, the method for manufacturing the cured material of the present invention preferably includes an exposure step of selectively exposing the film between the above-described film formation step and the above-described processing step, and the processing step is preferably a step of developing the film using the above-described processing solution as a developing solution to form a patterned film. Hereinafter, the state sample of performing the film formation step, the exposure step, and the developing step of developing the film using the processing solution as a developing solution to form a patterned film is also described as State Sample B. The exposure steps in the above-mentioned sample B are the same as those in the above-mentioned sample A, and the better sample is also the same. Except for the use of a processing solution as the developing solution, the developing steps in the above-mentioned sample B are the same as those in the above-mentioned sample A, and the preferred sample is also the same.

[0072] In the above-mentioned sample B, after the above-mentioned processing step (development step), a second processing step is further included, which involves contacting the second processing solution with the above-mentioned patterned film. It is preferable that the second processing solution contains at least one compound selected from the group consisting of alkaline compounds and alkali generating agents. The preferred embodiment of the composition and supply method of the second treatment liquid is the same as the preferred embodiment of the composition and supply method of the treatment liquid described above. Furthermore, it is also preferable that the second treatment solution mentioned above is a rinsing solution. Furthermore, the second processing step described above is preferably a rinsing step that cleans the patterned membrane with the aforementioned processing solution.

[0073] <Heating Steps> The method for manufacturing the hardened material of the present invention includes a heating step of heating the above-mentioned film. Furthermore, the method for manufacturing the hardened material of the present invention may include a heating step, which heats a pattern obtained by other methods without a developing step or a film obtained by a film forming step. During the heating step, resins such as polyimide precursors are cyclized to form resins such as polyimide. Furthermore, it also involves crosslinking unreacted crosslinking groups in specific resins or polymeric compounds other than specific resins. The preferred heating temperature (maximum heating temperature) in the heating step is 50~450℃, more preferably 120~230℃, and further preferably 150~230℃. To suppress wafer or panel warping, heating at a low temperature is preferred, with the preferred heating temperature (maximum heating temperature) being 150~200℃, more preferably 150~190℃, and further preferably 150~180℃.

[0074] The heating step is preferably a step of promoting the cyclization of the precursor of the cyclized resin in the membrane by heating, utilizing the action of at least one alkaline compound selected from the group consisting of the alkaline compound and the alkaline compound generated from the alkaline generating agent (i.e., the alkaline compound contained in at least one of the developing solution and the processing solution or the alkaline compound generated from the alkaline generating agent). The step of promoting the amide formation of the polyimide precursor in the membrane is even more preferred.

[0075] Regarding the heating process, it is preferable to increase the temperature at a rate of 1 to 12°C per minute from the initial temperature to the maximum heating temperature. A rate of 2 to 10°C per minute is more preferred, and 3 to 10°C per minute is even more preferable. By setting the heating rate to 1°C per minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C per minute or lower, residual stress in the hardened material can be mitigated. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0076] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, in the case of applying a resin composition to a substrate and then drying it, the temperature of the dried film (layer) is preferred, for example, starting the heating from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0077] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0078] In particular, when forming a multilayered body, from the viewpoint of interlayer tightness, a heating temperature of 30°C or above is preferred, 80°C or above is even better, 100°C or above is further preferred, and 120°C or above is especially preferred. The upper limit of the above heating temperature is preferably below 350°C, even better below 250°C, further better below 240°C, and best below 230°C. It can also be set to below 200°C or below 180°C.

[0079] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, and then increasing the temperature from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating the membrane with ultraviolet light. This pretreatment step can improve the membrane's properties. The pretreatment step can be performed in a short time, approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferred. The pretreatment can be performed in two or more stages; for example, the first stage of pretreatment can be performed in the range of 100–150°C, followed by the second stage of pretreatment in the range of 150–200°C. Furthermore, cooling can be performed after heating, and a cooling rate of 1~5℃ / minute is preferred at this time.

[0080] In terms of preventing the decomposition of certain resins, it is preferable to conduct the heating process in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon through the heating step and performing the process under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better. There are no particular limitations on the heating mechanism used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0081] <Post-development exposure steps> In addition to the heating step mentioned above, the film after the processing step can also be used in the post-exposure step of the pattern development after the exposure and development step. That is, the method for manufacturing the hardened material of the present invention may include a post-exposure step of developing the film after the exposure treatment step. In the post-development exposure step, it can promote, for example, the cyclization reaction of polyimide precursors by photoalkali generating agents or the removal of acid-degrading groups by photoacid generating agents. In the post-development exposure step, at least a portion of the film after the exposure treatment step is acceptable, but the entire film after the exposure treatment step is preferred. The exposure amount in the post-development exposure step is preferably 50~20,000 mJ / cm², and even better if the exposure energy is converted to the wavelength at which the photosensitive compound is sensitive. The post-development exposure step can be performed using the light source described in the above exposure step, with broadband light being preferable.

[0082] <Metal Layer Formation Steps> The film after the processing steps (preferably the film after the heating step) can be used in the metal layer forming step of forming a metal layer on the pattern. That is, the method for manufacturing the hardened material of the present invention preferably includes a metal layer forming step of forming a metal layer on the film (hardened material) after the processing step. Preferably, the film after the processing step is the film after the heating step.

[0083] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, with copper being even more preferred.

[0084] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), stripping, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited. As a preferred example of electroplating, electrolytic plating using copper sulfate or copper cyanide plating solutions can be cited.

[0085] For the thickness of the metal layer, a thickness of 0.01~50μm is preferred, and 1~10μm is even better.

[0086] <Applications> Examples of applications applicable to the manufacturing method of the cured material of the present invention or to the cured material of the present invention include insulating films for electronic components, interlayer insulating films for rewiring layers, and stress-relief films. Other applications include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed by etching insulating films used in practical mounting applications as described above. For these applications, please refer to, for example, Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and Japan Polyimide / Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0087] Furthermore, the manufacturing method of the hardened material of the present invention or the hardened material of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, in the application of etching forming components, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0088] (Laminated bodies and methods for manufacturing laminated bodies) The laminate of the present invention refers to a structure having a plurality of layers formed by the hardening material of the present invention. The laminate of the present invention is a laminate comprising two or more layers formed of a hardened material, and may also be a laminate consisting of three or more layers. In the above-mentioned laminate, at least one of the two or more layers formed by the above-mentioned hardener is a layer formed by the hardener of the present invention. From the viewpoint of suppressing the shrinkage of the hardener or the deformation of the hardener accompanying the shrinkage, it is also preferable that all the layers formed by the hardener in the above-mentioned laminate are layers formed by the hardener of the present invention.

[0089] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened material of the present invention, and it is even more preferable to include repeating the steps of the method for manufacturing the hardened material of the present invention a plurality of times.

[0090] The laminate of the present invention comprises two or more layers formed of a hardened material, and it is preferable that a metal layer is included between any one of the layers formed of the hardened material. Regarding the metal layer, it is preferable that it is formed by the aforementioned metal layer forming step. That is, the method for manufacturing the laminate of the present invention, between a plurality of processes for manufacturing a hardened material, preferably includes a metal layer forming step of forming a metal layer on the layer formed from the hardened material. The preferred form of the metal layer forming step is as described above. As an example of the aforementioned laminate, a laminate structure comprising at least three layers in sequence, namely a first layer formed of a hardener, a metal layer, and a second layer formed of a hardener, is preferred. Preferably, both the first layer formed by the cured material and the second layer formed by the cured material are layers formed by the cured material of the present invention. The resin composition used to form the first layer formed by the cured material and the resin composition used to form the second layer formed by the cured material can be composed of the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0091] <Layering Steps> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step includes a series of steps performed sequentially on the surface of the patterned (resin layer) or metal layer: (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) processing step, and (e) heating step. Alternatively, steps (a), (d), and (e) heating step can be repeated. Furthermore, after the heating step (e), a metal layer formation step (f) may be included. It is self-evident that the lamination step may further appropriately include the aforementioned drying step, etc.

[0092] If a further deposition step is performed after the deposition step, a surface activation treatment step can be performed after the aforementioned exposure step, the aforementioned heating step, or the aforementioned metal layer formation step. Plasma treatment can be exemplified as a surface activation treatment. Details of the surface activation treatment will be described later.

[0093] It is preferable to perform the above-mentioned layering steps 2 to 20 times, and even better to perform them 2 to 9 times. For example, in a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer configuration, it is preferable to have 2 or more resin layers and 20 or fewer resin layers, and it is even more preferable to have 2 or more resin layers and 9 or fewer resin layers. The composition, shape, and film thickness of each of the above layers can be the same or different.

[0094] In this invention, it is particularly preferred that the hardened form (resin layer) of the resin composition is formed by further covering the metal layer after the metal layer is formed. Specifically, examples include repeating the following steps in sequence: (a) film formation, (b) exposure, (c) development, (d) processing, (e) heating, and (f) metal layer formation. By alternating the lamination steps of the resin composition layer (resin layer) and the metal layer formation step, it is possible to alternately laminate the resin composition layer (resin layer) and the metal layer.

[0095] (Surface activation treatment step) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step can also be performed after the surface activation treatment step of the resin composition layer, after the development step described above. Regarding the surface activation treatment, it can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and it is preferable to perform surface activation treatment on a portion or all of the region of the metal layer on which the resin composition layer is formed. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved. Furthermore, it is preferable to perform surface activation treatment on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion between the resin layer and the metal layer disposed on the surface-activated surface can be improved. In particular, in cases where the resin composition layer hardens due to negative development, it is less susceptible to damage from the surface treatment, thereby easily improving adhesion. As a surface activation treatment, specifically, plasma treatment, corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, etc., selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixture, argon / oxygen mixture, etc.), surface treatment based on ultraviolet (UV) ozone method, immersion treatment in hydrochloric acid aqueous solution to remove oxide film followed by immersion in an organic surface treatment agent containing a compound having at least one amine group and a thiol group, and mechanical roughening treatment using a brush are preferred, especially oxygen plasma treatment using oxygen as the raw material gas. In the case of corona discharge treatment, an energy of 500~200,000 J / m2 is preferred, 1000~100,000 J / m2 is more preferred, and 10,000~50,000 J / m2 is optimal.

[0096] (Manufacturing methods for semiconductor devices) This invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing the cured material of this invention or the method for manufacturing the multilayer of this invention. For specific examples of semiconductor devices in which a resin composition is used in the formation of an interlayer insulating film for a redistribution layer, please refer to paragraphs 0213-0218 of Japanese Patent Application Publication No. 2016-027357 and Figure 1, and these contents are incorporated herein by reference.

[0097] (Resin composition) The resin composition is the resin composition used in the manufacturing method of the cured material of the present invention, the manufacturing method of the laminate of the present invention, or the manufacturing method of the semiconductor device of the present invention. The resin composition contains precursors of cyclized resins. The following is a detailed description of the components contained in the resin composition.

[0098] <Specific Resin> The resin composition of the present invention includes a precursor of a cyclized resin (a specific resin). Cyclic resins containing amide ring structures or oxazole ring structures in their main chain structure are preferred. In this invention, the main chain refers to the longest bond chain in the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide. Precursors to cyclized resins refer to resins that undergo chemical structural changes due to external stimuli to become cyclized resins. Resins that undergo chemical structural changes due to heat to become cyclized resins are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become cyclized resins are even better. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. That is, it is preferable that the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors and polyamide-imide precursors as the specific resin. The resin composition of the present invention preferably includes a polyimide precursor as a specific resin. Furthermore, it is preferable for a particular resin to have polymerizable groups, and even more preferable if it contains free radical polymerizable groups. When a particular resin has free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, depending on the need, it can include the sensitizer described later. Such a resin composition of the present invention can be used to form, for example, a negative photosensitive film. Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups. In cases where a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. Such a resin composition of the present invention can be used to form, for example, a chemically amplified positive or negative photosensitive film.

[0099] [Polyimide precursor] There are no special provisions regarding the type of polyimide precursor used in this invention, but it is preferable to include repeating units represented by the following formula (2). [Chemical Formula 5] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 independently represent hydrogen atoms or monovalent organic groups.

[0100] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, with oxygen atoms being preferred. In formula (2), R 111 represents 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 including 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, with groups comprising aromatic groups with 6 to 20 carbon atoms being more preferred. The aforementioned straight-chain or branched aliphatic groups can be substituted with groups whose hydrocarbon groups in the chain contain heteroatoms, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups whose cyclic hydrocarbon groups contain heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, particularly those represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is a group comprising a single bond, 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 combination of two or more of the above. These preferred ranges are as described above.

[0101] R 111 is preferably 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 may be used. Specifically, diamines comprising aliphatic groups having 2 to 20 carbon atoms (linear or branched), cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or combinations thereof, are preferred; diamines comprising aromatic groups having 6 to 20 carbon atoms are even more preferred. The aforementioned linear or branched aliphatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the chain, and the aforementioned cyclic aliphatic and aromatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the ring. Examples of groups comprising aromatic groups are as follows.

[0102] [Chemical Formula 6] In the formula, A represents a single bond or a divalent linker, preferably selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO 2-, -NHCO-, or combinations thereof. It is more preferred to select groups from alkyl groups with 1 to 3 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO 2-. -CH 2-, -O-, -S-, -SO 2-, -C(CF 3) 2-, or -C(CH 3) 2- are even more preferred. In the formula, * indicates the bonding location with other structures.

[0103] Specifically, diamines can be selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane 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'-diamine 3,3'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ketone or 3,3'-diaminodiphenyl ketone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy- 4-Aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) arsenide, bis(4-amino-3-hydroxyphenyl) arsenide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] arsenide, bis[4-(3-aminophenoxy)phenyl] arsenide, bis[4-(2-aminophenoxy)phenyl] arsenide, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl arsenide, 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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonate, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminophen, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2- bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl At least one diamine selected from the following: 3,4'-amino-2-trifluoromethylphenoxy)diphenyl benzoyl, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl benzoyl, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0104] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0105] Alternatively, it can be preferably used as a diamine having two or more alkyl diol units as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 on the main chain.

[0106] From the viewpoint of the flexibility of the obtained organic membrane, R 111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a group including an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenyl, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO 2-. Here, the aliphatic hydrocarbon group is preferably alkyl.

[0107] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R 111 is a divalent organogroup represented by formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organogroup represented by formula (61) is more preferable. Equation (51) [Chemical Formula 7] In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group. * represents the bonding site with the nitrogen atom in formula (2). Examples of monovalent organic groups in R 50 to R 57 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). [Chemical Formula 8] In formula (61), R 58 and R 59 are fluorine atoms, methyl or trifluoromethyl atoms, respectively, and * represents the bonding sites with nitrogen atoms in formula (2). Examples of diamines providing the structure of formula (51) or formula (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 in combination.

[0108] In formula (2), R 115 represents a tetravalent organogroup. As a tetravalent organogroup, a tetravalent organogroup containing an aromatic ring is preferred, and the group represented by formula (5) or formula (6) below is even more preferred. In equation (5) or equation (6), * independently represents the bonding location with other structures. [Chemical Formula 9] In formula (5), R 112 is a single bond or a divalent linker, preferably selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that are single bonds or can be substituted by fluorine atoms, -O-, -CO-, -S-, -SO 2- and -NHCO- and groups in combination thereof, preferably selected from a single bond, alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S- and -SO 2-, and even more preferably selected from divalent groups including -CH 2-, -C(CF 3) 2-, -C(CH 3) 2-, -O-, -CO-, -S- and -SO 2-.

[0109] Specifically, R115 can be exemplified by the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As the structure corresponding to R115, the polyimide precursor may contain only one type of tetracarboxylic acid dianhydride residue, or it may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 10] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.

[0110] 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 sulfide 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. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and such alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0111] Alternatively, the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as a better example.

[0112] In formula (2), at least one of R 111 and R 115 can also have an OH group. More specifically, as R 111, residues of diaminophenol derivatives can be cited.

[0113] In formula (2), R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group comprises a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and even more preferable that both contain polymerizable groups. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction 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, acetoxymethyl, epoxy, oxybutyl, benzo[a]azolyl, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred. 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)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with the group represented by formula (III) below being preferred.

[0114] [Chemical Formula 11]

[0115] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred. In equation (III), * indicates the bonding site with other structures. In formula (III), R 201 represents a alkyl group with 2 to 12 carbon atoms, -CH 2CH(OH)CH 2-, cycloalkyl group or polyalkylene group. Examples of preferred R 201 include alkylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH 2CH(OH)CH 2-, polyalkylene, alkylene, propylene, -CH 2CH(OH)CH 2-, cyclohexylene, polyalkylene, and alkylene, propylene, or polyalkylene are preferred, with alkylene, propylene, or polyalkylene being further preferred. In this invention, polyalkylene oxide refers to an alkylene oxide group directly bonded to two or more groups. The alkylene groups in the plurality of alkylene oxide groups contained in the polyalkylene oxide group may be the same or different. When a polyalkoxy group contains multiple alkoxy groups with different alkyl groups, the arrangement of the alkoxy groups in the polyalkoxy group can be random, block-shaped, or alternating. It is preferred that the carbon number of the above-mentioned alkyl group (in the case that the alkyl group has substituents, the carbon number including the substituents) is 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is the best. Furthermore, the aforementioned alkyl groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, it is preferable that the number of polyalkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups are preferred as polyvinyloxy groups. Polyvinyloxy or polypropyleneoxy is more preferred, and polyvinyloxy is even more preferred. Among the groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups, the ethyleneoxy and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred states of repeating ethyleneoxy groups are as described above.

[0116] In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylene unsaturated bond. An example of such a tertiary amine compound having an ethylene unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0117] In formula (2), at least one of R 113 and R 114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is a base-soluble group such as a phenolic hydroxyl group or a carboxyl group that decomposes under the action of acid. However, acetal, ketal, silyl alkyl, silyl ether, and tertiary alkyl ester groups are preferred. From the point of view of exposure sensitivity, acetal or ketal groups are more preferred. Specific examples of acid-degrading groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0118] Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more, and less than 20% by mass, is preferred in the polyimide precursor.

[0119] 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.

[0120] It is preferable that the repeating unit represented by formula (2) is 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 the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased. Equation (2-A) [Chemical Formula 12] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing polymerizable groups, preferably both of which are groups containing polymerizable groups.

[0121] A1, A2, R111, R113 and R114 have the same meaning as A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same. R 112 has the same meaning as R 112 in equation (5), and the preferred range is also the same.

[0122] Polyimide precursors may contain one repeating unit represented by formula (2), or two or more repeating units. They may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it is self-evident that polyimide precursors may contain other types of repeating units besides the repeating unit of formula (2).

[0123] As one embodiment of the polyimide precursor in this invention, an example is provided where the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is especially preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyimide precursor, except for the terminal units, can also be the repeating units represented by formula (2).

[0124] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. It is preferred that the molecular weight dispersion of the above-mentioned polyimide precursor is 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, for example, it is preferred to be 7.0 or lower, more preferably 6.5 or lower, and further preferably 6.0 or lower. In this specification, the molecular weight dispersion is a value calculated using the weight average molecular weight / number average molecular weight. 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. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are within the aforementioned ranges.

[0125] [Polybenzoxazole precursor] There are no special provisions regarding the structure of the polybenzoxazole precursor used in this invention, but it is preferred to include repeating units represented by the following formula (3). [Chemical Formula 13] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 represent hydrogen atoms or monovalent organic groups, respectively.

[0126] In equation (3), R123 and R124 have the same meaning as R113 in equation (2), and the preferred range is also the same. That is, it is preferred that at least one of them is a polymeric group. In formula (3), R 121 represents 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. Preferably, R 121 is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0127] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, with dicarboxylic acid residues containing aromatic groups being even more preferred. As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is even more preferred. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, 2 to 25 is more preferred, 3 to 20 is further preferred, 4 to 15 is even more preferred, and 5 to 10 is particularly preferred. The straight-chain aliphatic group is preferably an alkyl group. 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-tetrafluoroadipic acid. Methyl pimelic acid, 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, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

[0128] [Chemical Formula 14] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0129] As a dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids having only an aromatic group and two -COOH groups are even more preferred.

[0130] [Chemical Formula 15] In the formula, A represents a divalent group selected from the group consisting of -CH 2-, -O-, -S-, -SO 2-, -CO-, -NHCO-, -C(CF 3) 2- and -C(CH 3) 2-, and * represents the bonding site with other structures independently.

[0131] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and phthalic acid.

[0132] In equation (3), R 122 represents a tetravalent organogroup. As a tetravalent organogroup, it has the same meaning as R 115 in equation (2) above, and the preferred range is also the same. R 122 is preferably a group 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, 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.

[0133] Among diaminophenol derivatives, the following diaminophenol derivatives having aromatic groups are preferred.

[0134] [Chemical Formula 16] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group. Furthermore, R122 is also preferred for the structure represented by the above formula. In the case where R 122 is the structure represented by the above formula, it is preferable that any two of the four asterisks and # are bonded to the nitrogen atom of R 122 in formula (3) and the other two are bonded to the oxygen atom of R 122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom of R 122 in formula (3) and two # are bonded to the nitrogen atom of R 122 in formula (3). It is even more preferable that two asterisks are bonded to the nitrogen atom of R 122 in formula (3) and two # are bonded to the oxygen atom of R 122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom of R 122 in formula (3) and two # are bonded to the nitrogen atom of R 122 in formula (3).

[0135] The diaminophenol derivatives represented by formula (As) are also preferred. [Chemical Formula 17]

[0136] In formula (As), R1 is an organogroup selected from hydrogen atom, alkyl group, substituted alkyl group, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the group consisting of the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different.

[0137] [Chemical Formula 18] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0138] In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, will bring the carbonyl carbon of the amide bond closer to the hydroxyl group, which is particularly good in terms of further improving the effect of achieving a high cyclization rate when hardening at low temperature.

[0139] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it can maintain high transparency to i-rays and achieve a high cyclization rate when hardened at low temperature, which is therefore better.

[0140] Furthermore, in the above formula (As), it is even more preferable that R1 is an enyl alkyl group or a substituted enyl alkyl group. Specific examples of enyl alkyl groups and substituted enyl alkyl groups of R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of achieving a good balance between maintaining high transparency to i-rays and high cyclization rate during low-temperature curing and obtaining a polybenzoxazole precursor with sufficient solubility in solvents.

[0141] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, you can refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated into this specification.

[0142] Specific examples of the structures of diaminophenol derivatives represented by the above formula (As) can be found in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and such contents are incorporated herein by reference. Of course, it is self-evident that this is not the only possible embodiment.

[0143] In addition to the repeating unit in formula (3) above, polybenzoxazole precursors may also contain other types of repeating units. In terms of suppressing warping associated with ring closure, polybenzoxazole precursors preferably contain diamine residues represented by the following formula (SL) as other types of repeating units.

[0144] [Chemical Formula 19] In formula (SL), Z has an a structure and a b structure. R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R 2s is a hydrocarbon group with 1 to 10 carbon atoms, at least one of R 3s, R 4s, R 5s, and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups with 1 to 30 carbon atoms, which can be the same or different. The polymerization of the a structure and the b structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a structure is 5 to 95 molars, the b structure is 95 to 5 molars, and a+b is 100 molars.

[0145] In formula (SL), Z is preferably a structure where R5s and R6s are phenyl groups. Furthermore, the molecular weight of the structure shown in formula (SL) is preferably 400-4,000, and more preferably 500-3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzo[a]azole precursor after dehydration and ring closure can be reduced more effectively, achieving both the effect of suppressing warpage and improving solvent solubility.

[0146] In cases where the diamine residue represented by formula (SL) is used as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. As an example of such a tetracarboxylic acid residue, R 115 in formula (2) can be cited.

[0147] 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. 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. The molecular weight dispersion of the above-mentioned polybenzo[a]azole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and further preferably 1.6 or higher. There is no specific upper limit for the molecular weight dispersion of the polybenzo[a]azole precursor; for example, 2.6 or lower is preferred, 2.5 or lower is more preferred, 2.4 or lower is further preferred, 2.3 or lower is even more preferred, and 2.2 or lower is still even more preferred. Furthermore, when the resin composition includes multiple polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polybenzoxazole precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated using the multiple polybenzoxazole precursors as a single resin are within the aforementioned ranges.

[0148] [Polyamide imine precursor] It is preferable that the polyamide imide precursor contains repeating units represented by the following formula (PAI-2). [Chemical Formula 20] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.

[0149] In formula (PAI-2), R 117 can be an example of a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups by a single bond or by a linking group. It is preferred to obtain a group obtained by combining two or more of these groups by a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a single bond or by a linking group. It is even more preferred to obtain a group obtained by combining two or more of these groups by a single bond or by a linking group by an aromatic group having 6 to 20 carbons, or an aromatic group having 6 to 20 carbons. As the linking group mentioned above, it is preferred to form a linking group consisting of -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds, and it is even more preferred to form a linking group consisting of -O-, -S-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds. As the aforementioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred. As the aforementioned alkyl halides, alkyl halides with 1 to 20 carbon atoms are preferred, alkyl halides with 1 to 10 carbon atoms are more preferred, and alkyl halides with 1 to 4 carbon atoms are even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halides include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution of all hydrogen atoms with halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As described above, aryl, phenyl or naphthyl are preferred, phenyl is more preferred, and 1,3-phenyl or 1,4-phenyl are even more preferred.

[0150] Furthermore, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation described above. In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds. Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated. Examples of tricarboxylic acid compounds that can be halogenated and used in the manufacture of polyamide imine precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used in single or multiple forms.

[0151] Specifically, as a tricarboxylic acid compound, a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of these groups via a linker is preferred. A tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linker is even more preferred.

[0152] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 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 are linked by single bonds, -O-, -CH 2-, -C(CH 3) 2-, -C(CF 3) 2-, -SO 2-, or extended phenyl groups. These compounds can be compounds in which two carboxyl groups are anhydride-substituted (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride chloro).

[0153] In formula (PAI-2), R111, A2, and R113 have the same meaning as R111, A2, and R113 in formula (2) above, and the better state is also the same.

[0154] Polyamide imide precursors may further include other repeating units. Other repeating units can be exemplified by the repeating unit represented by equation (2) above, the repeating unit represented by equation (PAI-1) below, etc. [Chemical Formula 21]

[0155] In formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In formula (PAI-1), R 116 can represent a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups by a single bond or by a linking group. It is preferred to obtain a group obtained by combining two or more of these groups by a straight-chain aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or by combining two or more of these groups by a single bond or by a linking group. It is even more preferred to obtain a group obtained by combining two or more of these groups by a single bond or by combining two or more of these groups by a linking group by an aromatic group with 6 to 20 carbons. As the linking group mentioned above, it is preferred to form a linking group consisting of -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds, and it is even more preferred to form a linking group consisting of -O-, -S-, alkylene, alkyl halogenate, arylene, or two or more of the above-mentioned bonds. As the aforementioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred. As the aforementioned alkyl halides, alkyl halides with 1 to 20 carbon atoms are preferred, alkyl halides with 1 to 10 carbon atoms are more preferred, and alkyl halides with 1 to 4 carbon atoms are even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halides include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution of all hydrogen atoms with halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As described above, aryl, phenyl or naphthyl are preferred, phenyl is more preferred, and 1,3-phenyl or 1,4-phenyl are even more preferred.

[0156] Furthermore, R 116 is preferably derived from dicarboxylic acid compounds or dicarboxylic acid dihalides. In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide. In dicarboxylic acid dihalides, the carboxyl group only needs to be halogenated, for example, chlorination is preferred. That is, dicarboxylic acid dihalides are preferably dicarboxylic acid dichloride compounds. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that can be halogenated and used in the manufacture of polyamide imine precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in a single form or in two or more forms.

[0157] Specifically, as a dicarboxylic acid compound or dicarboxylic acid dihalide, it is preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide contains 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 single bond or a group obtained by combining two or more of these groups via a linking group. It is even more preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide contains an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linking group.

[0158] 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, heptafluoroadipic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, etc. Acid, hexafluorosebacic 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, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontandioic acid, triacontandioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyl diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, a compound with a structure formed by halogenating two carboxyl groups in the above-mentioned dicarboxylic acid compound examples can be cited.

[0159] In formula (PAI-1), R 111 has the same meaning as R 111 in formula (2) above, and the better state is also the same.

[0160] Furthermore, it is preferable that the polyamide imide precursor contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more in the polyamide imide precursor is preferred, and less than 20% by mass is even more preferred.

[0161] Furthermore, to improve adhesion to the substrate, the polyamide imine precursor can be copolymerized with an aliphatic group having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0162] As one embodiment of the polyamide imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; 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), formula (PAI-1), and formula (2). Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided where the total content of the repeating units represented by formula (PAI-2) and formula (PAI-1) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; 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) or formula (PAI-1).

[0163] 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. The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of the polyamide-imide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide-imide precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when considering the multiple polyamide-imide precursors as a single resin are within the above-mentioned ranges.

[0164] [Methods for manufacturing polyimide precursors, etc.] Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide and then esterifying it with a condensing agent or alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine. Among the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent, and then reacting it with diamine is preferred. Examples of condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of halogenating agents mentioned above include thiocyanate, oxalic acid, and phosphorus oxychloride. In methods for manufacturing polyimide precursors, it is preferable to use an organic solvent during the reaction. The organic solvent can be one type or two or more types. As an organic solvent, it can be appropriately selected according to the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In methods for manufacturing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types. The basic compound can be appropriately set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0165] -End- Capping Agent- In methods for manufacturing polyimide precursors, etc., it is preferable to seal the carboxylic anhydride, anhydride derivatives, or amine groups remaining at the resin ends of the polyimide precursor, etc., to further improve storage stability. When sealing the carboxylic anhydride and anhydride derivatives remaining at the resin ends, monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc., can be used as sealing agents. From the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are preferred. Preferred compounds as monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tertiary alcohols such as butanol and adamantanol. Preferred compounds among phenols include phenols, methoxyphenols, methylphenols, naphth-1-ols, naphth-2-ols, and hydroxystyrene. 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-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Naphthalene, 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 by reacting multiple end-capping agents, multiple different end groups can be introduced. Furthermore, when sealing the amine groups at the end of the resin, compounds with functional groups capable of reacting with the amine groups can be used for sealing. Preferred sealants for amine groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds as carboxylic acid chlorides include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, trimethylacetyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-adamantanemethyl chloride, heptafluorobutyric acid chloride, stearic acid chloride, and benzyl chloride.

[0166] -Solid precipitation- Methods for manufacturing polyimide precursors may include a step of precipitating a solid. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer components are added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer components to precipitate as a solid and then dried, thereby obtaining polyimide precursors. To improve purification, the operations of re-dissolving, re-precipitating, and drying the polyimide precursors may be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0167] 〔content〕 The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the resin composition, 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 is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The resin composition of the present invention may contain only one specific resin, or it may contain two or more resins. When two or more resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0168] Furthermore, it is preferable that the resin composition of the present invention contains at least two resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or it may contain two or more specific resins, but it is preferred to contain two or more specific resins. In the case where the resin composition of the present invention contains two or more specific resins, it is preferable to contain two or more polyimide precursors that are polyimide precursors and are derived from different structures of dianhydrides (R 115 described in formula (2) above).

[0169] <Other Resins> The resin composition of the present invention may include the specific resin described above and other resins that are different from the specific resin (hereinafter also referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxane or siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, amine resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins. 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 be obtained. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a (meth)acrylic resin with a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻³ moles / g or more) with a weight average molecular weight of 20,000 or less can be added to the resin composition, thereby improving the coatability of the resin composition, the solvent resistance of the pattern (cured material), etc.

[0170] When the resin composition of the present invention includes other resins, it is preferable that the content of other resins is 0.01% by mass or more relative to the total solid content of the resin composition, more preferably 0.05% by mass or more, further 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. Furthermore, it is preferable that the content of other resins in the resin composition of the present invention is 80% by mass or less relative to the total solid content of the resin composition, more preferably 75% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to provide an embodiment with a low content of other resins. In the above-mentioned embodiments, it is preferable that the content of other resins relative to the total solids content of the resin composition is 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When two or more other resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0171] <Polymerizable compounds containing urea bonds> The resin composition contains a polymeric compound having urea bonds (hereinafter also referred to as "polymeric compound U"). In this specification, unless otherwise specified, the term "polymeric compound" includes both the aforementioned polymeric compound U and other polymeric compounds described below. In this invention, the urea bond is represented by *-NR NU-C(=O)-NR NU-*, where R and NU independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom or a hydrogen atom, with at least one of * being a bonding site with a carbon atom. It is preferable that R and NU are hydrogen atoms or hydrocarbon groups, more preferably hydrogen atoms or alkyl groups, and even more preferably hydrogen atoms or methyl groups. Furthermore, a structure bonded to two * bonds can form a cyclic structure. Furthermore, even in the case of the aforementioned alkaline compounds or base generating agents containing amide groups (the group represented by *-NR NC(=O)-*), when both urea bonds and polymerizable groups are present, it is also designated as a polymerizable compound U. On the other hand, the aforementioned alkaline compounds or base generating agents containing amide groups include compounds containing amide groups that are not equivalent to polymerizable compound U.

[0172] There is no particular limitation on the number of urea bonds in the polymeric compound U, but more than one, 1 to 10 is preferred, 1 to 4 is even better, and 1 or 2 is further preferred.

[0173] Polymerizable compound U is a compound containing urea bonds and polymerizable groups. Examples of polymerizable groups include free radical polymerizable groups, acetomethyl, hydroxymethyl, hydroxyethyl, alkoxymethyl, epoxy, oxybutyl, benzo[a]azolyl, etc., with free radical polymerizable groups being preferred. As a free radical polymerizable group, it is preferable to have a group containing an ethylene unsaturated bond. Examples of such groups containing an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acrylyl, maleicadiimino, and (meth)acrylamine groups, which are groups containing ethylene unsaturated bonds. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the groups containing vinyl unsaturated bonds, and (meth)acryl is more preferred from the viewpoint of reactivity.

[0174] There is no particular limitation on the number of polymerizable groups in the polymerizable compound U, but more than one, 1 to 10 is preferred, 1 to 4 is even more preferred, and 1 or 2 is even more preferred. Furthermore, a state containing a monofunctional polymerizable compound having only one polymerizable group as polymerizable compound U is also one of the preferred states of the present invention.

[0175] The preferred free radical polymerizability value (mass of the compound per 1 mol of free radical polymerizability) in polymerizable compound U is 150~400 g / mol. The lower limit of the free radical polymerizability value is preferably 200 g / mol or higher, 210 g / mol or higher is even better, 220 g / mol or higher is even better, 230 g / mol or higher is even better, 240 g / mol or higher is particularly good, and 250 g / mol or higher is optimal. The upper limit of the free radical polymerizability value is preferably below 350 g / mol, further preferably below 330 g / mol, and especially preferably below 300 g / mol. By setting the free radical polymerizability value above the lower limit, the chemical resistance of the cured material tends to be good, and by setting the free radical polymerizability value below the upper limit, the developability tends to be good. Among them, the polymerizability value of the polymerizable compound U is preferably 210~400 g / mol, and even more preferably 220~400 g / mol.

[0176] The polymeric compound U is preferably represented by the structure of the following formula (U-1). [Chemical Formula 22] In formula (U-1), R U1 is independently a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1-valent organic group, X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer from 1 to 10.

[0177] In formula (U-1), R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and a hydrogen atom is even more preferred. In formula (U-1), Z U1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2-, -NR NZU-, or a group obtained by bonding two or more of these groups. It is even more preferred that a hydrocarbon group or a group obtained by bonding a hydrocarbon group with at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) 2-, and -NR NZU- is bonded. RN represents a hydrogen atom or a monovalent organic group; a hydrogen atom or a hydrocarbon group is preferred, an alkyl group is more preferred, and a hydrogen atom or a methyl group is further preferred. As for the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is even more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by such bonds. In formula (U-1), Z U2 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2-, -NR NZU-, or a group obtained by bonding two or more of these groups, and it is even more preferable that the hydrocarbon group or the hydrocarbon group is bonded to at least one group selected from the group including -O-, -C(=O)-, -S-, -S(=O) 2- and -NR NZU-. As for the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is even more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by such bonds. In formula (U-1), X is not particularly limited, but examples include vinyl, allyl, (meth)acryl, (meth)acryloxy, (meth)acrylamine, vinylphenyl, maleic anhydride, etc., with (meth)acryloxy, (meth)acrylamine, vinylphenyl or maleic anhydride being preferred, and (meth)acryloxy being even more preferred. In formula (U-1), n ​​is a better integer from 1 to 10, a better integer from 1 to 4, a further better integer from 1 or 2, and an especially better integer from 1. In equation (U-1), m is preferably an integer from 1 to 10, even better is an integer from 1 to 4, and 1 is even better.

[0178] It is also preferred that the polymeric compound U has at least one of the following groups: hydroxyl, alkoxy, amide, and cyano. From the perspective of the chemical resistance of the obtained hardened film, the hydroxyl group can be either an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred. From the viewpoint of the chemical resistance of the obtained hardened film, as an alkoxy group, an alkoxy group with 2 to 20 carbon atoms is preferred, an alkoxy group with 2 to 10 carbon atoms is more preferred, an alkoxy group with 2 to 4 carbon atoms is more preferred, an ethyl or propyl group is further preferred, and an ethyl group is particularly preferred. The alkoxy group can be included as a polyalkoxy group in the polymeric compound U. A repetition number of 2 to 10 is preferred, and 2 to 6 is even more preferred. The amide group refers to the bond represented by -C(=O)-NR N-. As mentioned above, RN represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. When the polymeric compound U has an amide group, the polymeric compound U can, for example, be included as a group represented by RC(=O)-NR N-* or *-C(=O)-NR NR. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. The polymeric compound U may have two or more structures selected from the group consisting of hydroxyl, pentaalkoxy (wherein, in the case of constituting polypentaalkoxy), amide and cyano groups, but a state having only one structure in the molecule is also one of the preferred states of the present invention. The aforementioned hydroxyl, (poly)-alkoxy, amide, and cyano groups can be present at any position in the polymeric compound U. However, from the viewpoint of drug resistance, a preferred embodiment of the present invention is a structure in which the polymeric compound U comprises at least one group selected from the group consisting of the aforementioned hydroxyl, (poly)-alkoxy, amide, and cyano groups, and is connected to at least one free radical polymeric group contained in the polymeric compound U via a linker containing a urea bond (hereinafter also referred to as "linker L2-1"). In particular, when the polymerizable compound U contains only one free radical polymerizable group, it is preferable that the free radical polymerizable group contained in the polymerizable compound U is linked to at least one of the groups selected from the group consisting of hydroxyl, (poly)alkoxy, amide and cyano groups by a linking group containing a urea bond (hereinafter also referred to as "linking group L2-2"). In the case where the polymerizable compound U contains an alkoxy group (wherein, in the case of constituting a polyalkoxy group, it is a polyalkoxy group) and has the aforementioned linker L2-1 or linker L2-2, the structure of the alkoxy group (wherein, in the case of constituting a polyalkoxy group, it is a polyalkoxy group) bonded to the side opposite to linker L2-1 or linker L2-2 is not particularly limited, but groups represented by hydrocarbon groups, free radical polymerizable groups, or combinations thereof are preferred. As the aforementioned hydrocarbon group, hydrocarbon groups with 20 or fewer carbon atoms are preferred, hydrocarbon groups with 18 or fewer carbon atoms are more preferred, and hydrocarbon groups with 16 or fewer carbon atoms are even more preferred. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by such bonds. Also, the preferred form of the free radical polymerizable group is the same as the preferred form of the free radical polymerizable group in the aforementioned polymerizable compound U. When the polymerizable compound U contains a amide group and has the aforementioned linker L2-1 or linker L2-2, the structure of the bond between the amide group and the side opposite to linker L2-1 or linker L2-2 is not particularly limited, but a hydrocarbon group, a free radical polymerizable group, or a combination thereof is preferred. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by such bonds. Also, the preferred form of the free radical polymerizable group is the same as the preferred form of the free radical polymerizable group in the aforementioned polymerizable compound U. Furthermore, in the above-mentioned state, the carbon atom side of the amide group can be bonded to linker L2-1 or linker L2-2, and the nitrogen atom side of the amide group can also be bonded to linker L2-1 or linker L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of voids in wiring (especially suppression of Cu voids in copper wiring), polymeric compound U having hydroxyl groups is preferred.

[0179] From the perspective of compatibility with specific resins, it is preferable for polymeric compound U to contain aromatic groups. It is preferable that the aromatic group is directly bonded to the urea bond contained in the polymerizable compound U. When the polymerizable compound U contains two or more urea bonds, it is preferable that one of the urea bonds is directly bonded to the aromatic group. The aromatic group can be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a structure that forms a condensed ring from these, but an aromatic hydrocarbon group is preferred. As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is even more preferred, and a group obtained by removing two or more hydrogen atoms from the benzene ring structure is even more preferred. As the aforementioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of aromatic heterocycles in such groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, acetazole, isoacetazole, thiazole, pyridine, pyrimidine, pyrazine, triazine, etc. These rings can be further condensed with other rings, such as indole and benzimidazole. Furthermore, nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups. It is preferable that the aforementioned aromatic group is included, for example, in a linker group that connects two or more free radical polymerizable groups and includes a urea bond, or in a linker group that connects at least one of the groups selected from the group consisting of hydroxyl, alkoxy, amide and cyano groups to at least one free radical polymerizable group contained in the polymerizable compound U.

[0180] There is no particular limitation on the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group in the polymerizable compound U, but 30 or less is preferred, 2 to 20 is more preferred, and 2 to 10 is even more preferred. When the polymerizable compound U contains at least one of two or more urea bonds and a polymerizable group, the minimum number of atoms (connecting chain length) between the urea bond and the free radical polymerizable group is acceptable as long as it falls within the above-mentioned range. In this specification, "the number of atoms between the urea bond and the polymerizable group (linkage chain length)" refers to the shortest (minimum number of atoms) atomic chain connecting the two atoms or groups of atoms in the path connecting the linked objects. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloxy) is 2. [Chemical Formula 23]

[0181] [Axis of symmetry] Compounds with a structure that does not have a symmetry axis are also preferred for polymerizability. The absence of a symmetry axis in polymeric compound U means that rotating the compound as a whole does not produce a molecular axis identical to that of the original molecule, resulting in asymmetry. Furthermore, when the structural formula of polymeric compound U is written on paper, the absence of a symmetry axis means that the structural formula of polymeric compound U cannot be written in a way that displays a symmetry axis. It is believed that by using polymeric compound U, which does not have a symmetry axis, the aggregation of polymeric compounds U in the composition film can be suppressed.

[0182] [Molecular weight] The molecular weight of the polymeric compound U is preferably 100-2,000, preferably 150-1,500, and even more preferably 200-900.

[0183] [physical properties] The SP (solution parameter) value of the polymerizable compound U is preferably 17~30MPa 0.5, more preferably 18~28MPa 0.5, and further preferably 19~27MPa 0.5. Furthermore, it is preferable that the absolute value of the difference between the SP value of the alkaline compound or alkali generating agent contained in the treatment solution and the SP value of the polymerizable compound U is 1~8 MPa 0.5, more preferable that is 1~7 MPa 0.5, and even more preferable that is 1~5 MPa 0.5. When the treatment solution contains multiple alkaline compounds and alkali generating agents, it is preferable that the absolute value of the difference between the SP value of at least one of them and the SP value of the polymerizable compound U is within the above-mentioned range. In this specification, the SP value is the Hansen dissolution parameter (unit: (MPa) 0.5), and it is calculated using the Hansen dissolution parameter calculation software "HSPiP ver.5.1.02".

[0184] The CLogP value of polymerizable compound U is preferably -1 to 6, more preferably 0 to 5, and even more preferably 1 to 4. Furthermore, it is preferable that the absolute value of the difference between the CLogP value of the alkaline compound or alkali generating agent contained in the treatment solution and the CLogP value of the polymerizable compound U is 1 to 6, 1 to 5 is even better, and 1 to 4 is even more preferred. When the treatment solution contains multiple basic compounds and alkali generating agents, it is preferable that the absolute value of the difference between at least one CLogP value and the CLogP value of the polymerizable compound U is within the above-mentioned range. In this specification, “logP” represents the logP (log[water / octanol partition coefficient]) calculated based on the chemical structure. The ClogP used in this specification is the value calculated using Chem Draw Pro 20.1.1.

[0185] [Manufacturing Method] There is no particular limitation on the method of manufacturing polymeric compound U, but it can be obtained, for example, by reacting a compound having a free radical polymeric compound and an isocyanate group with a compound having at least one of a hydroxyl or an amino group.

[0186] [Specific example] Specific examples of polymerizable compound U are shown below, but polymerizable compound U is not limited thereto. [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26]

[0187] The content of polymeric compound U relative to the total solids content of the resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The resin composition may contain only one polymeric compound U, or it may contain two or more polymeric compounds U. When it contains two or more polymeric compounds U, it is preferable that their total content is within the above range.

[0188] <Other polymeric compounds> The resin composition of the present invention may further include other polymeric compounds. The other polymeric compounds mentioned above do not include compounds corresponding to polymeric compound U. Other examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0189] [Free radical crosslinking agent] It is preferable that the resin composition of the present invention contains a free radical crosslinking agent. Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, the free radical polymerizable group contains an ethylene unsaturated bond. Examples of such ethylene unsaturated bond groups include vinyl, allyl, vinylphenyl, (meth)acryl, maleicadiimino, and (meth)acrylamine groups. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the groups containing vinyl unsaturated bonds, and (meth)acryl is more preferred from the viewpoint of reactivity.

[0190] Free radical crosslinking agents are preferably compounds with one or more vinyl unsaturated bonds, but compounds with two or more are even more preferred. Free radical crosslinking agents can have three or more vinyl unsaturated bonds. As for the 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 even more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (hardened material), it is preferable that the resin composition of the present invention contains compounds having two ethylene unsaturated bonds and the aforementioned compounds having three or more ethylene unsaturated bonds.

[0191] The molecular weight of the free radical crosslinking agent is preferably below 2,000, more preferably below 1,500, and even more preferably below 900. The lower limit of the molecular weight of the free radical crosslinking agent is preferably above 100.

[0192] Specific examples of free radical crosslinking agents 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 polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl or amino groups, or hydrogen sulfide groups, with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, 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, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyl groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Additionally, as another example, compounds that replace the aforementioned unsaturated carboxylic acids can be used, such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and such contents are incorporated into this specification.

[0193] Furthermore, it is preferable that the free radical crosslinking agent is a compound with a boiling point above 100°C at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetra(meth)acrylate, neopentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl)isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols to form ethylene oxide or propylene oxide, followed by (methyl) crosslinking. Compounds obtained by esterification of acrylic acid, such as (meth)acrylate amino esters described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, and polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, as well as epoxy acrylates and other multifunctional acrylates or methacrylates as products of the reaction between epoxy resin and (meth)acrylic acid, and mixtures thereof. Furthermore, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Alternatively, examples include polyfunctional (meth)acrylates obtained by reacting compounds such as glycidyl (meth)acrylate, which have cyclic ether groups and vinyl unsaturated bonds, with polyfunctional carboxylic acids.

[0194] Furthermore, as a preferred free radical crosslinking agent besides the above, compounds having a cycloid and having two or more groups containing ethylene unsaturated bonds, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

[0195] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Additionally, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0196] In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be used more readily, and such contents are incorporated into this specification.

[0197] Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compound, which is described together with specific examples as formula (1) and formula (2), can also be used as a free radical crosslinking agent. This compound is obtained by (meth)acrylate esterification after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0198] 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 such contents are incorporated into this specification.

[0199] As free radical crosslinking agents, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and structures in which the (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0200] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethynooxy chains) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (difunctional methyl acrylates with four ethoxy chains) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentynooxy chains) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutyryloxy chains); ethyl carbamate 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). Products manufactured by Kyoisha Chemical Co., Ltd. include UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), and BLEMMER PME400 (manufactured by NOF CORPORATION).

[0201] As free radical crosslinking agents, amine ester acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and amine ester compounds with an ethylene oxide backbone described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0202] Free radical crosslinking agents can be those containing acid groups such as carboxyl or phosphate groups. It is preferable that the free radical crosslinking agent containing acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. It is even more preferable that the free radical crosslinking agent containing acid groups is formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent containing acid groups formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., such as M-510 and M-520.

[0203] The preferred acid value of a free radical crosslinking agent containing an acid group is 0.1~300 mg KOH / g, and the particularly preferred acid value is 1~100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the manufacturing process is excellent, and consequently, the developability is excellent. Furthermore, the polymerizability is good. The above acid value is determined according to the description in JIS K 0070:1992.

[0204] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. 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-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Dimethacrylates, dimethyloltricyclodecane dimethacrylates, dimethyloltricyclodecane dimethacrylates, ethylene oxide (EO) adduct dimethacrylates of bisphenol A, propylene oxide (PO) adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylates, cyanuric acid (EO) modified dimethacrylates, cyanuric acid modified dimethacrylates, difunctional acrylates having other amine ester bonds, and difunctional methacrylates having amine ester bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of approximately 200. Regarding the resin composition of the present invention, from the viewpoint of suppressing warpage by controlling the elastic modulus of the accompanying pattern (cured material), a monofunctional free radical crosslinking agent can be preferably used as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, alkenyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, compounds with a boiling point of over 100°C at normal pressure are preferred in order to suppress volatilization before exposure. In addition, as free radical crosslinking agents with two or more functions, examples include allyl compounds such as diallyl phthalate and trimellitic acid triallyl ester.

[0205] In the case of a free radical crosslinking agent, it is preferable that its content relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0206] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more at the same time, it is better to keep the total dosage within the above range.

[0207] [Other crosslinking agents] It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. It is preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the photosensitive acid generator or photobase generator mentioned above. It is also preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the action of acid or base. It is preferable that the acid or base mentioned above is generated from the photoacid generator or photoalkali generator during the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred. Other crosslinking agents include, for example, compounds having a structure in which hydrogen atoms of the amine groups are replaced by acetoxymethyl, hydroxymethyl, or alkoxymethyl groups through reaction of formaldehyde or formaldehyde and alcohol with melamine, glycourea, urea, alkyl urea, benzoguanamine, or other amine-containing compounds. 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. Alternatively, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used. Crosslinking agents that use melamine as the above-mentioned amine-containing compounds are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkyl urea are called urea-based crosslinking agents; crosslinking agents that use alkyl urea are called alkyl urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents. In these respects, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0208] As a compound containing at least one of the alkoxymethyl and acetoxymethyl groups of the present invention, examples of compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted on the nitrogen atom or triatom of the aromatic group or the urea structure described below are provided as structural examples. It is preferred that the alkoxymethyl or acetomethyl group in the above compounds has 2 to 5 carbon atoms, 2 or 3 carbon atoms are preferred, and 2 carbon atoms are even more preferred. It is preferable that the total number of alkoxymethyl and aceoxymethyl groups in the above compounds is 1 to 10, more preferably 2 to 8, and especially preferably 3 to 6. The molecular weight of the above-mentioned compounds is preferably below 1500, and 180 to 1200 is preferred.

[0209] [Chemical Formula 27]

[0210] R 100 indicates alkyl or acetylated. R 101 and R 102 each independently represent a monovalent organic group and can bond together to form a ring.

[0211] As compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group, examples include various compounds of the following general formula.

[0212] [Chemical Formula 28]

[0213] In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl or acetyl group, and R 103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce a base-soluble group (e.g., a group that is released under the action of an acid, or a group represented by -C(R 4) 2COOR 5 (R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is released under the action of an acid.)). R 105 independently represents alkyl or alkenyl groups, 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. Regarding groups that decompose under the action of acid to produce base-soluble groups, groups that are removed under the action of acid, and the R5 in the group represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In the formula, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can bond together to form a ring. As the aforementioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms are even more preferred. The aforementioned alkyl group can be either straight-chain or branched. 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 even more preferred. The aforementioned cycloalkyl groups can be monocyclic structures or polycyclic structures such as condensed rings. The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and phenyl is even more preferred. Aryl groups with 7 to 20 carbon atoms are preferred, and aryl groups with 7 to 16 carbon atoms are even more preferred. The aforementioned aryl group refers to an aryl group substituted with an alkyl group, and the preferred state of such alkyl and aryl groups is the same as that of the aforementioned alkyl and aryl groups. The alkenyl group with 3 to 20 carbon atoms is preferred, and the alkenyl group with 3 to 16 carbon atoms is even more preferred. Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0214] R 01 and R 02 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl or alkenyl groups, respectively.

[0215] These groups are preferably trialkyl esters, acetals, cumyl esters, or enols. More preferably, they are trialkyl esters or acetals.

[0216] Specifically, the following structures can be cited as examples of compounds having an alkoxymethyl group. Regarding compounds having an acetoxymethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group can be cited. Various compounds can be cited as examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule, but the list is not limited to these.

[0217] [Chemical Formula 29]

[0218] [Chemical Formula 30]

[0219] For compounds containing at least one of alkoxymethyl and aceoxymethyl, commercially available ones or those synthesized by known methods may be used. From the perspective of heat resistance, compounds in which alkoxymethyl or acetomethyl groups are directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0220] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0221] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc. Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea. Ethylene urea, including monohydroxymethylated ethoxyurea, dihydroxymethylated ethoxyurea, monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, diethoxymethylated ethoxyurea, monopropoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea, and dibutoxymethylated ethoxyurea, are ethoxyurea-based crosslinking agents. Monohydroxymethylated linalourea, dihydroxymethylated linalourea, monomethoxymethylated linalourea, dimethoxymethylated linalourea, monoethoxymethylated linalourea, diethoxymethylated linalourea, monopropoxymethylated linalourea, dipropoxymethylated linalourea, monobutoxymethylated linalourea, or dibutoxymethylated linalourea are all linalourea-based crosslinking agents. 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0222] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, and monomethoxymethylated benzoguanidine. Dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, etc.

[0223] In addition, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethyl phenyl ester, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenyl Methyl ketone, methoxymethylbenzoic acid methoxymethylphenyl ester, 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.

[0224] Other commercially available crosslinking agents can also be used. Among preferred commercially available agents are 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.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0225] Furthermore, it is preferable that the resin composition of the present invention includes at least one compound selected from the group consisting of epoxy compounds, cyclobutane compounds and benzo[a] compounds as other crosslinking agents.

[0226] -Epoxy compounds (compounds containing epoxy groups)- As an epoxy compound, compounds having two or more epoxy groups per molecule are preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, the presence of an epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

[0227] The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warpage. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

[0228] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl 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, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones with epoxy groups such as polymethyl(glycidyloxypropyl)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, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel). (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 (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds can also be used more preferably.

[0229] [Chemical Formula 31]

[0230] In the formula, n is an integer from 1 to 5 and m is an integer from 1 to 20.

[0231] Among the above structures, considering both heat resistance and elongation, n = 1~2 and m = 3~7 are preferred.

[0232] -Oxycyclic butane compounds (compounds containing oxycyclic butane groups)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutane)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred, and two or more of these can be used alone or in combination.

[0233] -Benzoquinone compounds (compounds containing a benzoquinone group)- Because the cross-linking reaction is caused by the ring-opening addition reaction, the benzo[a] compound does not produce degassing during hardening, thereby further reducing thermal shrinkage and inhibiting warping, and is therefore preferred.

[0234] Preferred examples of benzo[a] compounds include Pd-type benzo[a], Fa-type benzo[a], (the above are product names, manufactured by Shikoku Chemicals Corporation), benzo[a] adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a] compounds. These can be used alone or in combination of two or more.

[0235] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, further preferably 0.5-15% by mass, and particularly preferably 1.0-10% by mass. The other crosslinking agents may be only one type or may contain two or more types. When two or more other crosslinking agents are contained, it is preferable that their total content falls within the above-mentioned range.

[0236] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferable to contain a photopolymerization initiator. Photopolymerization initiators are preferably photoradical polymerization initiators. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light in the ultraviolet to visible regions are preferred. Alternatively, it can be an activator that interacts with a photoexcited sensitizer to generate active free radicals.

[0237] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L / mol⁻¹ / cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0238] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a trihalomethyl skeleton, compounds with a diazole skeleton, compounds with a trihalomethyl skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron-aromatic complexes, etc. For details regarding 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, the contents of which are incorporated herein by reference. Furthermore, examples can be cited in 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 peracid-based initiators described in Japanese Patent Application Publication No. 2019-167313, and these contents are also incorporated into this specification.

[0239] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611 can be cited, and this content is incorporated into this specification. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0240] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine 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 amide phosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated into this specification.

[0241] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0242] 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 (all manufactured by BASF) can be used.

[0243] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0244] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

[0245] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0246] Oxime compounds are a better example of photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wider exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly advantageous.

[0247] 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 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.

[0248] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoxyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propoxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoxyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonoxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, the use of oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators is particularly preferred. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker within the molecule.

[0249] [Chemical Formula 32]

[0250] 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, the photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structures can also be used. [Chemical Formula 33]

[0251] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, and these contents are incorporated into this specification.

[0252] As a photoradical polymerization initiator, oxime compounds having at least one benzene ring in the carbazole ring as the naphthalene ring skeleton 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.

[0253] Furthermore, 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, and these contents are included in this specification.

[0254] Nitro-containing oxime compounds can be used as photopolymerization initiators. It is also preferable that the nitro-containing oxime compound is a dimer. Specific examples of nitro-containing oxime compounds include the compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012 and 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 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) can also be cited as a nitro-containing oxime compound.

[0255] 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.

[0256] As a photoradical polymerization initiator, 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, and this content is included in this specification.

[0257] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group Ar OX1 with an electron-withdrawing group introduced onto the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic Ar OX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred for the ease of forming a film with excellent lightfastness, with benzoyl being even more preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio or amino are even more preferred, and alkoxy, alkylthio or amino are further preferred.

[0258] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 34] In the formula, R X1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphine, aminomethyl, or aminosulfonyl. RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino. RX3 to RX14 represent hydrogen atoms or substituents independently, respectively. Among them, at least one of RX10 to RX14 is an electron-withdrawing group.

[0259] In the above formula, it is preferable that RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are hydrogen atoms.

[0260] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

[0261] Examples of optimal oxime compounds include those with specific substituents as shown in Japanese Patent Application Publication No. 2007-269779 or those with thioaryl groups as shown in Japanese Patent Application Publication No. 2009-191061, and these are included in this specification.

[0262] From the perspective of exposure sensitivity, photoradical polymerization initiators are preferably compounds selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetylsphine 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, halomethyl acetic acid diazole compounds, and 3-aryl substituted coumarin compounds.

[0263] A further preferred photoradical polymerization initiator is a trihalomethane trihalomethane compound, an α-aminoketone compound, an acetophosphine 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, preferably selected from at least one compound selected from the group consisting of trihalomethane trihalomethane compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds, and even more preferably, a metallocene compound or an oxime compound is used.

[0264] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones 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. Additionally, compounds represented by formula (I) below can also be used.

[0265] [Chemical Formula 35]

[0266] In formula (I), RI00 is an alkyl group with 1 to 20 carbon atoms, an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbon atoms or a phenyl group, or an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group with 2 to 12 carbon atoms, an alkyl group with 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group with 1 to 4 carbon atoms, at least one of which is a phenyl or biphenyl group. RI01 is a group represented by formula (II) or a group that is the same as RI00. RI02 to RI04 are each independently an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms or a halogen atom.

[0267] [Chemical Formula 36]

[0268] In the formula, R I05~R I07 are the same as R I02~R I04 in the above formula (I).

[0269] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, and this content is incorporated into this specification.

[0270] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators 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 ( ) described in Japanese Patent Application Publication No. 2013-522445. G) Cmpd1-7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent No. 6469669, etc., and these contents are incorporated into this specification.

[0271] 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, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount within the above-mentioned range is preferred. Furthermore, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0272] [Thermal polymerization initiator] It is also preferable that the resin composition of the present invention contains a thermal polymerization initiator. As a thermal polymerization initiator, it can be selected according to the type of polymerizable compound, but thermal free radical polymerization initiators are preferred. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy and initiate or promote the polymerization reaction of polymerizable compounds. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization by heat, and can sometimes be added as thermal polymerization initiators.

[0273] Examples of known azo compounds and peroxide compounds can be cited as thermal polymerization initiators. Examples of azo compounds include azobisides. Azo compounds can be compounds containing a cyano group or compounds without a cyano group. Examples of peroxide compounds include ketone peroxides, peroxy acetals, hydroperoxides, dialkyl peroxides, diacyl peroxides, dicarbonates, and peroxide esters. Commercially available products can also be used as thermal polymerization initiators, such as V-40, V-601, and VF-096 manufactured by FUJIFILM Wako Pure Chemical Corporation, and PERHEXYL O, PERHEXYL D, PERHEXYL I, PERHEXA 25O, PERHEXA 25Z, PERCUMYL D, PERCUMYL D-40, PERCUMYL D-40MB, PERCUMYL H, PERCUMYL P, and PERCUMYL ND. Furthermore, as a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited, and this content is incorporated into this specification.

[0274] The content of the thermal polymerization initiator in the resin composition is preferably 0.05% by mass or more and 10% by mass or less relative to the total solid content of the composition, more preferably 0.1% by mass or more and 10% by mass or less, further preferably 0.1% by mass or more and 5% by mass or less, and especially preferably 0.5% by mass or more and 3% by mass or less. The resin composition may contain only one type of thermal polymerization initiator, or it may contain two or more types. When it contains two or more types, it is preferable that their total amount is within the range mentioned above.

[0275] [Sensitizer] The resin composition may include sensitizers. Sensitizers absorb specific active radiation to become electronically excited. These electronically excited sensitizers then come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heat generation. Consequently, the thermal free radical polymerization initiators and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole azomethine, phthalocyanine, benzopyran, and indigo can be used. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallyl dihydroindone, and p-dimethylamino Benzylene dihydroindone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3-ethoxy 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-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamine Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Alternatively, other sensitizing pigments can be used. For details regarding the sensitized pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

[0276] When the resin composition contains a sensitizer, the sensitizer content 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 further preferably 0.5 to 10% by mass. A single sensitizer may be used, or two or more may be used simultaneously.

[0277] [Chain transfer agent] The resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd 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, dithioaminocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0278] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0279] 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 further 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, it is preferable that their total content is within the above-mentioned range.

[0280] [Photoacid generator] It is preferable that the resin composition of the present invention contains a photoacid generating agent. A photoacid generator is a compound that produces at least one of Bristol acid and Lewis acid upon irradiation with light in the range of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator capable of producing acid upon photosensitization is preferred. Examples of acids produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonic acid amides.

[0281] Examples of photoacid generators used in the resin composition of this invention include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfonic acid compounds, and onium salts. From the perspective of sensitivity and storage stability, organohalogen compounds, oxime sulfonates, and onium salts are preferred; from the perspective of the mechanical properties of the formed film, oxime esters are preferred.

[0282] Examples of quinone diazide compounds include those obtained by attaching a sulfonate ester to a monovalent or polyvalent hydroxyl compound, those obtained by attaching a sulfonic acid to a monovalent or polyvalent amine compound via a sulfonylurea bond, and those obtained by attaching a sulfonic acid to a polyhydroxy polyamine compound via an ester bond and / or a sulfonylurea bond. Examples of the aforementioned quinone diazides include 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazides, but it is preferable that at least 40 moles of the total functional groups are substituted with quinone diazides. By containing such a quinone diazide compound, a resin composition capable of photosensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a typical ultraviolet mercury lamp can be obtained.

[0283] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tributanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, and BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu) (Manufactured by Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.) Co., Ltd. manufactures phenolic varnish resins, 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirodi(1H-indene)-5,5',6,6',7,7'hexanol, etc., but not limited to these.

[0284] Examples of amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, etc., but are not limited to these.

[0285] Furthermore, examples of polyhydroxy polyamine compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited to these.

[0286] Among these, compounds containing phenolic compounds and esters with 4-naphthoquinone diazidesulfonyl groups are preferred as quinone diazide compounds. This allows for higher sensitivity and higher resolution to i-ray exposure.

[0287] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is therefore preferable. Furthermore, sensitizers or the like can be added as needed.

[0288] It is preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound"). There are no particular restrictions on the presence of an oxime sulfonate group in the oxime sulfonate compound, but examples include those described in paragraphs 0118 to 0124 of International Publication No. 2020 / 195995. This content is incorporated into this specification.

[0289] Alternatively, the following compounds represented by the structural formulas can be cited as better examples. [Chemical Formula 37]

[0290] Examples of organohalogenated compounds include those described in paragraphs 0042-0043 of Japanese Patent Application Publication No. 2015-087409. This content is incorporated into this specification.

[0291] Examples of organoborate compounds include, for instance, those described in paragraph 0055 of Japanese Patent Application Publication No. 2015-087409. This content is incorporated into this specification.

[0292] Examples of diazonium compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2002-328465, as well as diazonium compounds.

[0293] Examples of the aforementioned onium salt compounds include, for instance, the diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980); the ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; the phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; the phosphonium salts described in European Patent Nos. 104,143, 339,049, and 410,201; the phosphonium salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and the phosphonium salts described in European Patent Nos. 370,693 and 3... The strontium salts described in the specifications of patents 90,214, 233,567, 297,443, 297,442, US patents 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, German patents 2,904,626, 3,604,580, and 3,604,581, and JVCrivello... Selenium salts described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), are included in this specification.

[0294] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, further preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass. A photoacid generator can be used alone or in combination with multiple agents. When multiple agents are used in combination, the total amount is preferably within the range mentioned above. Furthermore, it is better to use it in conjunction with a sensitizer in order to impart photosensitivity to the desired light source.

[0295] <Alkali-generating agents> The resin composition of the present invention may include an alkali generating agent. The alkali generating agent is 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. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By including a thermal alkali-generating agent in the resin composition, such as one that can promote the cyclization reaction of the precursor by heating, the mechanical properties or chemical resistance of the cured material are improved, for example, its performance as an interlayer insulating film for redistribution layers included in semiconductor packages becomes better. As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include secondary and tertiary amines. There are no particular limitations on the alkali-generating agent of the present invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid acetamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and acetoimine compounds. Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3). [Chemical Formula 38]

[0296] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Rb1 and Rb2 do not simultaneously constitute hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not possess a carboxyl group. Moreover, in this specification, a tertiary amine structure refers to a structure where all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0297] In formulas (B1) and (B2), it is preferable that at least one of Rb1, Rb2, and Rb3 contains a cyclic structure, and it is even more preferable that at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. It is preferable that the monocyclic ring is a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. It is preferable that the monocyclic ring is a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0298] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and further preferably with 6-10 carbon atoms), or aralkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and further preferably with 7-12 carbon atoms). These groups may have substituents within the range that enables the effects of the present invention. Rb1 and Rb2 may be bonded to each other to form a ring. A nitrogen-containing heterocycle with 4-7 members is preferred as the formed ring. In particular, Rb 1 and Rb 2 are preferably straight-chain, branched or cyclic alkyl groups (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons) that may have substituents, preferably cycloalkyl groups (preferably with 3 to 24 carbons, more preferably with 3 to 18 carbons, and even more preferably with 3 to 12 carbons), and preferably cyclohexyl groups that may have substituents.

[0299] Furthermore, the state in which at least one of Rb 1 and Rb 2 has an amino group is also one of the preferred states of the present invention. Specifically, for example, one could cite the case where at least one of Rb 1 and Rb 2 is a group represented by the following formula (R-1). [Chemical Formula 39] In formula (R-1), R R1 represents a divalent organic group, R R2 represents a monovalent organic group, X represents a amide group, and * represents a bonding site with other structures. In formula (R-1), R1 is preferably a hydrocarbon group or a group represented by a hydrocarbon group bonded to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -SO2-, and -NR-. R represents a hydrogen atom or a monovalent organic group; a hydrogen atom or a hydrocarbon group is preferred, a hydrogen atom or an alkyl group is more preferred, and a hydrogen atom is even more preferred. Preferably, the bonding sites between L1 and the two nitrogen atoms are both hydrocarbon groups. The hydrocarbon group in R R1 above can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is even more preferred. Furthermore, the hydrocarbon group can also have known substituents within the scope of achieving the effects of the present invention. In formula (R-1), the orientation of the amino group in X is not particularly limited. The amino group in X can bond with R and R1 on the carbon atom side or on the nitrogen atom side. In formula (R-1), R2 is preferably a hydrocarbon group or a group represented by a hydrocarbon group bonded to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -SO2- and -NR-. The R mentioned above is the same as the R in R1 mentioned above, and the preferred state is also the same. The hydrocarbon group in R and R2 described above can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred. Furthermore, the hydrocarbon group can also have known substituents within the scope of achieving the effects of the present invention. [Chemical Formula 40]

[0300] Furthermore, it is also preferable that the group represented by formula (R-1) is the same as the group represented by formula (R-2) below. [Chemical Formula 41] In formula (R-2), R R1 represents a divalent organic group, R R3 represents a hydrogen atom or a methyl group, and * represents a bonding site with other structures.

[0301] In equation (R-2), the preferred state of R R1 is the same as the preferred state of R R1 in equation (R-1).

[0302] Examples of Rb 3 include alkyl groups (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), aryl groups (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-10 carbons), alkenyl groups (preferably with 2-24 carbons, more preferably with 2-12 carbons, and further preferably with 2-6 carbons), and aralkyl groups (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). The preferred groups are aryl (preferably 8-24 carbons, more preferably 8-20, and further preferably 8-16 carbons), alkoxy (preferably 1-24 carbons, more preferably 2-18, and further preferably 3-12 carbons), aryloxy (preferably 6-22 carbons, more preferably 6-18, and further preferably 6-12 carbons), or arylalkoxy (preferably 7-23 carbons, more preferably 7-19, and further preferably 7-12 carbons). Cycloalkyl (preferably 3-24 carbons, more preferably 3-18, and further preferably 3-12 carbons), aryl, and arylalkoxy groups. Rb3 may also have substituents within the scope of the effects of this invention.

[0303] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 42]

[0304] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 have the same meaning as Rb 1 and Rb 2 in formula (B1). Rb 13 is an alkyl group (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an alkenyl group (preferably with 2-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). Substituents may be present within the scope of the effects of this invention. Preferably, Rb 13 is an aralkyl group.

[0305] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbons, more preferably with 1 to 8 carbons, and even more preferably with 1 to 3 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 8 carbons, and even more preferably with 2 to 3 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), and a hydrogen atom is preferred.

[0306] Rb 35 is alkyl (preferably with 1-24 carbons, more preferably with 1-12 carbons, and even more preferably with 3-8 carbons), alkenyl (preferably with 2-12 carbons, more preferably with 2-10 carbons, and even more preferably with 3-8 carbons), aryl (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-12 carbons), aralkyl (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons), with aryl being preferred.

[0307] Furthermore, the compound represented by formula (B1-1) is also preferred over the compound represented by formula (B1-1a). [Chemical Formula 43]

[0308] Rb 11 and Rb 12 have the same meaning as Rb 11 and Rb 12 in equation (B1-1). Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 6 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 6 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), hydrogen atoms, or methyl groups are preferred. Rb 17 is an alkyl group (preferably with 1-24 carbons, more preferably with 1-12 carbons, and further preferably with 3-8 carbons), an alkenyl group (preferably with 2-12 carbons, more preferably with 2-10 carbons, and further preferably with 3-8 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons), wherein an aryl group is preferred.

[0309] [Chemical Formula 44]

[0310] In formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group with a divalent saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is three or more. Furthermore, RN1 and RN2 each independently represent a monovalent organic group.

[0311] In this specification, a "linking chain" refers to an atomic chain that connects two atoms or groups of atoms in the shortest possible (minimum number of atoms) path. For example, in the compound represented by the following formula, L is composed of phenyl-ethyl and has ethyl as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms in the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length") is 4. [Chemical Formula 45]

[0312] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. An upper limit of 12 or less is more preferred, 10 or less is further preferred, and 8 or less is especially preferred. A lower limit of 4 or more is more preferred. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, an upper limit of 12 or less of the linking chain length of L is preferred, 8 or less is more preferred, 6 or less is further preferred, and 5 or less is especially preferred. In particular, a linking chain length of 4 or 5 is preferred, with 4 being optimal. Specific 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.

[0313] Furthermore, it is preferable that the alkali generating agent contains a compound represented by the following formula (N1). [Chemical Formula 46]

[0314] In formula (N1), RN1 and RN2 independently represent monovalent organic groups, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0315] L is a divalent linker, and a divalent organic group is preferred. A linker chain length of 1 or more is preferred, and 2 or more is even better. As an upper limit, 12 or less is preferred, 8 or less is even better, and 5 or less is further preferred. The linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0316] In formula (N1), RN1 and RN2 independently represent monovalent organic groups (preferably with 1-24 carbon atoms, more preferably with 2-18, and further preferably with 3-12 carbon atoms) and hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10 carbon atoms). Specifically, aliphatic hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10) or aromatic hydrocarbon groups (preferably with 6-22 carbon atoms, more preferably with 6-18, and further preferably with 6-10 carbon atoms) are preferred. If aliphatic hydrocarbon groups are used as RN1 and RN2, the resulting base has high basicity, which is therefore preferred. Furthermore, aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can be in the aliphatic hydrocarbon chain or the aromatic ring, with oxygen atoms in the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0317] Examples of aliphatic hydrocarbon groups constituting RN1 and RN2 include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Straight-chain or branched chain alkyl groups having 1 to 24 carbon atoms are preferred, 2 to 18 are more preferred, and 3 to 12 are even more preferred. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, dibutyl, tributyl, isopentyl, neopentyl, tripentyl, and isohexyl. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Groups relating to combinations of chain alkyl and cyclic alkyl groups are preferably composed of 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups relating to combinations of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. It is preferred that the alkyl group having oxygen atoms in the chain 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. From the viewpoint of increasing the boiling point of the alkali produced by decomposition (described later), it is preferable that RN1 and RN2 are alkyl groups with 5 to 12 carbon atoms. In formulations where close adhesion with metals (e.g., copper) is important, groups with cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms are preferred.

[0318] RN1 and RN2 can be interconnected to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, the ring structure formed by RN1 and RN2 can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the formed ring structure, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. Examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperidine rings, and morpholine rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperidine rings, and morpholine rings are particularly preferred. Furthermore, it is preferable that at least one of RN1 and RN2 is a group represented by formula (R-1) above, and it is even more preferable that the group represented by formula (R-2) above is also a group represented by formula (R-2) above.

[0319] R C1 represents a hydrogen atom or a protecting group, with hydrogen atom being preferred.

[0320] As a protecting group, a protecting group that can be decomposed by the action of acid or base is preferred, and a protecting group that can be decomposed by acid can be given as an example.

[0321] 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, tributyl, and cyclohexyl. Specifically, examples of chain-like alkyl groups having oxygen atoms in the chain include alkyloxyalkyl groups, and more specifically, examples include methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP).

[0322] There are no particular restrictions on the type of linker constituting the divalent L, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is even more preferred. The hydrocarbon group may have substituents and may also contain atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linker having an oxygen atom in the chain is preferred; groups relating to 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 having an oxygen atom in the chain are even more preferred; a divalent aliphatic hydrocarbon group having an oxygen atom in the chain is further preferred. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group (e.g., arylalkyl) related to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0323] As the linking group L, specifically, linear or branched chain alkyl groups, cyclic alkyl groups, groups relating to combinations of linear and cyclic alkyl groups, alkyl groups having oxygen atoms in the chain, linear or branched chain alkenyl groups, cyclic alkenyl groups, aryl groups, and aryl alkyl groups are preferred. It is preferred that the linear or branched alkyl groups have 1 to 12 carbon atoms, 2 to 6 carbon atoms are more preferred, and 2 to 4 carbon atoms are even more preferred. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even better. It is preferred that the groups associated with the combination of chain-like and cyclic-like alkyl groups have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkyl group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. It is preferred that the alkyl group containing oxygen atoms in the chain has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

[0324] The linear or branched chain-like alkenyl group having 2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, and 2 to 3 is even more preferred. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferred to be 1 to 10, 1 to 6 is more preferred, and 1 to 3 is even more preferred. Cyclic alkenyl groups with 3 to 12 carbon atoms are preferred, and 3 to 6 carbon atoms are even more preferred. The number of C=C bonds in the cyclic alkenyl groups is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl group with 6 to 22 carbon atoms is preferred, 6 to 18 is even better, and 6 to 10 is even more preferred. The arylalkyl group having 7 to 23 carbon atoms is preferred, 7 to 19 is even better, and 7 to 11 is further preferred. Among them, chain-like alkyl groups, cyclic alkyl groups, alkyl groups having oxygen atoms in the chain, chain-like alkenyl groups, aryl groups, aryl groups, and alkyl groups are preferred, and 1,2-ethylenyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylenyl (especially cis-vinylenyl), phenylenyl (1,2-phenylenyl), phenylmethylene (especially 1,2-phenylmethylene), and oxyethylenyl (especially 1,2-ethoxy-1,2-ethylenyl) are even more preferred.

[0325] Examples of alkali-generating agents can be given below, but the present invention is not limited thereto.

[0326] [Chemical Formula 47]

[0327] The molecular weight of the nonionic hot alkali generator is preferably below 800, more preferably below 600, and further preferably below 500. As a lower limit, 100 or above is preferred, 200 or above is more preferred, and 300 or above is further preferred.

[0328] Preferred compounds for use as ionic base generators include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0329] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 48]

[0330] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 49]

[0331] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of resin in the resin composition of the present invention. A lower limit of 0.3 parts by weight or more is more preferred, and 0.5 parts by weight or more is further preferred. An upper limit of 30 parts by weight or less is more preferred, 20 parts by weight or less is further preferred, 10 parts by weight or less is even more preferred, and it can be 5 parts by weight or less, or 4 parts by weight or less. One or more alkali-generating agents can be used. When using two or more, it is preferable to keep the total dosage within the above-mentioned range.

[0332] Solvent The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, and alcohols.

[0333] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid)). Ethyl esters, etc.), alkyl esters of 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., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

[0334] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether 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.

[0335] Among the ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone are preferred examples.

[0336] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are good examples.

[0337] As a class of urethanes, dimethyl urethane can be cited as a preferred example.

[0338] Among the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxymorpholine, and N-acetymorpholine are considered as preferred choices.

[0339] Among urea compounds, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are considered to be better choices.

[0340] 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 monopropylene 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, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0341] Regarding solvents, from the perspective of improving the properties of the coating surface, it is better to mix two or more forms.

[0342] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucanone, and dihydroglucanone, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

[0343] From a coating properties perspective, it is preferable to set the solvent content to a total solids concentration of 5-80% by mass in the resin composition of the present invention, more preferably to a concentration of 5-75% by mass, further preferably to a concentration of 10-70% by mass, and even more preferably to a concentration of 20-70% by mass. The solvent content can be adjusted according to the desired coating thickness and coating method.

[0344] The resin composition of this invention may contain only one solvent or two or more solvents. When containing two or more solvents, it is preferable that the total number of solvents falls within the above-mentioned range.

[0345] <Metal adhesion modifier> The resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonylurea structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0346] [Silane coupling agent] 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, and these contents 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. Also, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0347] [Chemical Formula 50]

[0348] 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-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane. Trimethoxysilane, 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-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0349] [Aluminum-based adhesives] Examples of aluminum-based adhesives include aluminum tri(ethyl acetate)aluminum, tri(ethyl acetone)aluminum, and aluminum diisopropoxide of ethyl acetate.

[0350] 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 may also be used, and such contents are incorporated into this specification.

[0351] 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 in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion modifier, or there may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0352] <Migration Inhibitors> It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0353] There are no particular limitations on the use of compounds as migration inhibitors, but examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, succinazole ring, thiazole ring, pyrazole ring, isosuccinazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine 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.

[0354] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0355] Other migration inhibitors may be used, including the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073-0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, and these contents are incorporated into this specification.

[0356] The following compounds can be cited as specific examples of migration inhibitors.

[0357] [Chemical Formula 51]

[0358] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid 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.

[0359] Migration inhibitors can be one or more. When there are two or more migration inhibitors, it is preferable that their total number falls within the above-mentioned range.

[0360] <Polymerization Inhibitor> 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.

[0361] Specific compounds that are polymerization inhibitors can be the same as those contained in the above-described treatment solution. For example, molecules with small molecular weights and high volatility are preferred. Specifically, molecules with a molecular weight below 300 are preferred, and those below 200 are even better.

[0362] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid 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.

[0363] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that the total number is within the above range.

[0364] <Other Additives> The resin composition of this invention can be incorporated with various additives as needed, within the scope of achieving the effects of this invention, such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane can be adjusted. Regarding these components, for example, reference can be made to paragraph 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, and these contents are incorporated herein by reference. When these additives are incorporated, it is preferable that the total amount incorporated is 3% by mass or less of the solid content of the resin composition of the present invention.

[0365] [Surfactants] As surfactants, various surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. These surfactants can be nonionic, cationic, or anionic.

[0366] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) during preparation as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid is reduced, improving the wettability of the coated surface and thus improving the coating properties. Therefore, it is possible to form a film with a more uniform thickness and smaller thickness non-uniformity.

[0367] Examples of fluorinated surfactants include 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 (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (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 OMNOVA Solutions Inc.), etc. Fluorinated surfactants may also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, and these contents are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and such contents are incorporated into this specification. Fluorinated surfactants can also preferably use fluorinated polymers, which contain repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propyleneoxy groups). Examples of fluorinated surfactants used in this invention include the following compounds. [Chemical Formula 52]

[0368] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorinated surfactants can also be used to treat fluoropolymers with vinyl unsaturated groups on their side chains. 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. Commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

[0369] Fluorinated surfactants are preferably composed of 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants within this fluorine content range are effective in terms of uniformity of coating thickness and liquid-saving properties, and also exhibit good solubility in the composition.

[0370] 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 Corning Toray 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-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0371] 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 & FAT CO.,LTD.).

[0372] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. As commercially available products, examples 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 Co., Ltd.), etc.

[0373] As cationic surfactants, examples include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), and W001 (manufactured by Yusho Co.,Ltd.).

[0374] As anionic surfactants, examples include WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0375] A single surfactant can be used, or two or more surfactants can be used in combination. The surfactant content relative to the total solids content of the composition is preferably 0.001~2.0% by mass, and even more preferably 0.005~1.0% by mass.

[0376] [Higher fatty acid derivatives] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide can be added to the resin composition of the present invention, so that they exist unevenly on the surface of the resin composition of the present invention during the drying process after coating.

[0377] Furthermore, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 may also be used for higher fatty acid derivatives, and such content is incorporated into this specification.

[0378] When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solids 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, it is preferable that their total content is within the above-mentioned range.

[0379] [Thermal polymerization initiator] The resin composition of this invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization through heat, and can sometimes be added as thermal polymerization initiators.

[0380] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as initiators of thermal free radical polymerization, and this content is incorporated into this specification.

[0381] 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 may contain two or more types. When two or more thermal polymerization initiators are included, the total amount within the above-mentioned range is preferred.

[0382] [Inorganic particles] The resin composition of this invention may contain inorganic particles. Specifically, these 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, boron nitride, etc.

[0383] The average particle size of the aforementioned inorganic particles is preferably 0.01~2.0 μm, more preferably 0.02~1.5 μm, further preferably 0.03~1.0 μm, and especially preferably 0.04~0.5 μm. The average particle size of the inorganic particles mentioned above is the primary particle size and is the volume average particle size. The volume average particle size can be determined by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In cases where the above determination is difficult, it can also be determined by centrifugal sedimentation transmission, X-ray transmission, or laser diffraction / scattering.

[0384] [Ultraviolet absorber] The resin composition of this invention may contain a UV absorber. As a UV absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based UV absorbers can be used. 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.

[0385] Examples of acrylonitrile-based UV absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triphenyl terpenoid ultraviolet absorbers include mono(hydroxyphenyl)triphenyl compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl. 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triphenyl, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl, etc., are bis(hydroxyphenyl)triphenyl compounds; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triphenyl, etc., are tri(hydroxyphenyl)triphenyl compounds, etc.

[0386] In the resin composition of the present invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more. The resin composition of the present invention may or may not contain ultraviolet absorbers, but when it does contain ultraviolet absorbers, it is preferable that the content of ultraviolet absorbers is 0.001% by mass or more and 1% by mass or less relative to the total solid content of the resin composition of the present invention, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[0387] [Organotitanium compounds] The resin composition of this invention may contain organotitanium compounds. Because the resin composition contains organotitanium compounds, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0388] As usable organotitanium compounds, examples include those in which the organic group is bonded to titanium atoms via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds with two or more alkoxy groups are preferred, as they exhibit excellent preservation stability of the resin composition and can achieve good curing patterns. Specific examples include diisopropanol bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropanol bis(2,4-pentanedione) titanium, diisopropanol bis(tetramethylheptanedione) titanium, and diisopropanol bis(ethyl acetate) titanium. II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenyl oxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc. III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc. V) Titanium oxide compounds: such as titanium dioxide bis(pentanedione), titanium dioxide bis(tetramethylheptanedione), phthalocyanine titanium dioxide, etc. VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc. VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonate titanate, etc.

[0389] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds and III) diacetic titanium compounds is preferred as an organotitanium compound. In particular, diisopropanol bis(acetyl ethyl acetate)titanium, tetra(n-butanol)titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

[0390] When an organotitanium compound is incorporated, the amount of incorporation is preferably 0.05 to 10 parts by weight relative to 100 parts by weight of a specific resin, and more preferably 0.1 to 2 parts by weight. When the amount of incorporation is 0.05 parts by weight or more, the resulting hardened pattern exhibits better heat resistance and chemical resistance. On the other hand, when the amount of incorporation is 10 parts by weight or less, the preservation stability of the composition is more excellent.

[0391] [Antioxidants] The resin composition of this invention may contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and its adhesion to metallic materials 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, a hindered phenolic compound can be mentioned. Compounds having a substituent at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both phenolic and phosphite groups within the same molecule are also preferred as antioxidants. Furthermore, 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]dioxaphosphine-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-heptacyclic-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, and this content is incorporated into this specification. Additionally, the resin composition of the present invention may contain potential antioxidants as needed. As potential antioxidants, compounds whose antioxidant activity is achieved by the removal of the protecting group at the site of antioxidant action can be cited, and which exert their antioxidant activity by heating at 100-250°C or at 80-200°C in the presence of an acid / base catalyst to remove the protecting group. As potential antioxidants, compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 can be cited, and these contents are incorporated herein by reference. Commercially available products as potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0392] [Chemical Formula 53]

[0393] In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R7 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or an organogroup containing at least one of an oxygen atom and a nitrogen atom in a 1 to 4 valence. k represents an integer from 1 to 4.

[0394] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0395] It can act on both resin and metal materials simultaneously, therefore, k being an integer from 2 to 4 is preferred. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and it may also have substituents. Among these, from the viewpoint of solubility in the developer and metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion during the formation of metal complexes, -NH- is more preferred.

[0396] Regarding the compounds represented by general formula (3), the following can be cited as examples, but are not limited to the following structures.

[0397] [Chemical Formula 54]

[0398] [Chemical Formula 55]

[0399] [Chemical Formula 56]

[0400] [Chemical Formula 57]

[0401] The amount of antioxidant added relative to the resin is preferably 0.1 to 10 parts by weight, and 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 effect of improving elongation characteristics or adhesion to metal materials, even under high temperature and high humidity environments. Furthermore, by setting the amount added to 10 parts by weight or less, the sensitivity of the resin composition can be improved, for example, through interaction with photosensitizers. Only one type of antioxidant may be used, or two or more types may be used. When using two or more types, the total amount within the above-mentioned range is preferred.

[0402] [Anticoagulant] The resin composition of this invention may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0403] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination. The resin composition of the present invention may or may not contain an anti-coagulant. However, when it does contain an anti-coagulant, it is preferable that the content of the anti-coagulant is 0.01% by mass or more and 10% by mass or less relative to the total solid content of the resin composition of the present invention, and more preferably 0.02% by mass or more and 5% by mass or less.

[0404] [Phenolic compounds] The resin composition of this invention 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 tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

[0405] In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The resin composition of the present invention may contain phenolic compounds or may not contain phenolic compounds. However, when phenolic compounds are included, it is preferable that the content of phenolic compounds is 0.01% by mass or more and 30% by mass or less relative to the total solid content of the resin composition of the present invention, and more preferably 0.02% by mass or more and 20% by mass or less.

[0406] [Other polymers] Other examples of polymeric compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyren...

Claims

1. A method for manufacturing a hardened material, comprising: The membrane forming step involves applying a resin composition comprising a precursor of a cyclized resin and a polymerizable compound having urea bonds and free radical polymerizable groups onto a substrate to form a membrane; the processing step involves contacting a processing liquid with the aforementioned membrane; and the heating step involves heating the aforementioned membrane after the aforementioned processing step, wherein the aforementioned processing liquid comprises at least one compound selected from the group consisting of basic compounds and alkali-generating agents.

2. The method for manufacturing a hardened material as claimed in claim 1, wherein between the aforementioned film formation step and the aforementioned processing step, there is an exposure step of selectively exposing the aforementioned film and a development step of developing the exposed film with a developer to form a patterned film.

3. The method for manufacturing the hardened material as described in claim 1, wherein the aforementioned processing liquid is a rinsing liquid.

4. The method for manufacturing the hardened material as described in claim 1, wherein the aforementioned processing step is a rinsing step of cleaning the aforementioned membrane with the aforementioned processing solution.

5. The method for manufacturing a hardened material as claimed in claim 1, wherein between the aforementioned film formation step and the aforementioned processing step, there is an exposure step for selectively exposing the aforementioned film, and the aforementioned processing step is a step of developing the aforementioned film by using the aforementioned processing solution as a developing solution to form a patterned film.

6. The method for manufacturing a hardened material as claimed in claim 5, wherein after the aforementioned processing step, a second processing step is further included in which a second processing liquid is brought into contact with the aforementioned patterned film, the aforementioned second processing liquid comprising at least one compound selected from the group consisting of alkaline compounds and alkali generating agents.

7. A method for manufacturing a hardened material as described in any one of claims 2 to 6, wherein the aforementioned development is negative development.

8. A method for manufacturing a hardened compound as described in any one of claims 1 to 6, wherein the aforementioned polymeric compound having a urea bond comprises a monofunctional polymeric compound having only one polymeric group.

9. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned resin composition further comprises a polymerization initiator.

10. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned alkaline compound is an amine and the aforementioned alkali generating agent is a compound that generates an amine.

11. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned alkaline compound is a secondary or tertiary amine, and the aforementioned alkali generating agent is a compound that generates a secondary or tertiary amine.

12. A method for manufacturing a hardened compound as described in any one of claims 1 to 6, wherein the aforementioned alkaline compound is an alkaline compound having an amino group, and the aforementioned alkali generating agent is an alkali generating agent having an amino group.

13. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned alkaline compound and the aforementioned alkali generating agent have an acrylamide group or a methacrylamide group.

14. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned processing liquid further contains a polymerization inhibitor.

15. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the material comprises 50% by mass or more of an organic solvent relative to the total mass of the aforementioned processing liquid.

16. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the precursor of the aforementioned cyclized resin is a polyimide precursor.

17. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the aforementioned heating step is a step of promoting the cyclization of the precursor of the aforementioned cyclized resin by heating using the action of at least one alkaline compound selected from the group consisting of the aforementioned alkaline compound and alkaline compounds generated from the aforementioned alkaline generating agent.

18. A method for manufacturing a hardened material as described in any one of claims 1 to 6, wherein the heating temperature in the aforementioned heating step is 120 to 230°C.

19. A method for manufacturing a laminate, comprising a method for manufacturing a hardened material as described in any one of claims 1 to 18.

20. The method for manufacturing a laminate as described in claim 19, further comprising a metal layer forming step of forming a metal layer on the hardened material between repeated operations of the aforementioned method for manufacturing a hardened material.

21. A method for manufacturing a semiconductor device, comprising a method for manufacturing a hardened material as described in any one of claims 1 to 18, or a method for manufacturing a multilayer as described in claim 19 or 20.

22. A treatment fluid used in a method for manufacturing a hardened material, the method comprising: The membrane forming step involves applying a resin composition comprising a precursor of a cyclized resin and a polymerizable compound having urea bonds and free radical polymerizable groups onto a substrate to form a membrane; the processing step involves contacting a processing liquid with the aforementioned membrane; and the heating step involves heating the aforementioned membrane after the aforementioned processing step, wherein the processing liquid comprises at least one compound selected from the group consisting of basic compounds and alkali-generating agents.

23. The processing solution as described in claim 22, wherein the method for manufacturing the aforementioned hardened material further includes an exposure step of selectively exposing the film formed by the aforementioned film forming step and a developing step of developing the exposed film by a developing solution to form a patterned film, wherein the aforementioned processing step is a rinsing step of cleaning the aforementioned patterned film by the aforementioned processing solution.

24. A resin composition comprising a precursor of a cyclized resin and a polymerizable compound having urea bonds and free radical polymerizable groups, and provided in a method for manufacturing a cured article, the method comprising: The film forming step involves applying the aforementioned resin composition onto a substrate to form a film. The processing step involves bringing the processing solution into contact with the aforementioned membrane; The process includes a heating step, in which the membrane is heated after the aforementioned processing steps.

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