Methods for manufacturing cured materials, methods for manufacturing multilayers, methods for manufacturing semiconductor devices, resin compositions, cured materials, multilayers, and semiconductor devices

Abstract

This invention provides a method for manufacturing a cured product with minimal gas release, a method for manufacturing a laminate using the above-described method for manufacturing the cured product, and a method for manufacturing a semiconductor device. It also provides a resin composition that produces minimal gas release from the obtained cured product, a cured product formed by curing the resin composition, a laminate containing the cured product, and a semiconductor device. The method for manufacturing the cured product includes a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and a heating step of heating the film at a heating temperature of 180°C or lower. The glass transition temperature of the obtained cured product is 200°C or higher.

Description

[Technical Field]

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

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

[0003] For example, in the above-described applications, cyclic resins such as polyimide are used in the form of a resin composition comprising at least one of a cyclic resin such as polyimide and a precursor of a cyclic resin. For example, such a resin composition is applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc., as needed, thereby forming a cured material on the substrate. The precursor of the aforementioned cyclic resin, such as the polyimide precursor, is cyclized by heating to become a cyclic resin such as polyimide in the cured material. The resin composition can be applied by known coating methods, etc., therefore, it can be said that the design freedom of the applied resin composition, such as its shape, size, and application position, is high, and its manufacturing adaptability is excellent. Considering that in addition to the high performance of cyclic resins such as polyimide, such excellent manufacturing adaptability is also present, the expansion of industrial applications of the above-described resin composition is increasingly promising.

[0004] For example, Patent Document 1 describes a semiconductor device characterized by having a semiconductor wafer, a sealing material covering the semiconductor wafer, and a redistribution layer with an area larger than the semiconductor wafer when viewed from above, wherein the weight reduction rate of the interlayer insulating film of the redistribution layer after being heated to 700°C at 10°C / min in an air environment is 5 to 95% by weight.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-113748 [Summary of the Invention]

[0006] In methods for obtaining a cured article by curing a resin composition containing a cyclized resin precursor, it is sometimes desirable to produce less gas release from the cured article. The object of the present invention is to provide a method for manufacturing a cured article that produces less gas release, a method for manufacturing a multilayer using the above-described method for manufacturing a cured article, and a method for manufacturing a semiconductor device. Furthermore, the object of the present invention is to provide a resin composition that produces less gas release from the obtained cured article, a cured article obtained by curing the above-described resin composition, a multilayer containing the above-described cured article, and a semiconductor device.

[0007] Hereinafter, examples of representative embodiments of the present invention are shown. <1> A method for manufacturing a cured material, comprising: a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film; and a heating step of heating the film at a heating temperature of 180°C or lower, wherein the glass transition temperature of the resulting cured material is 200°C or higher. <2> The method for manufacturing a cured material as described in <1>, wherein the heating temperature is 170°C or lower. <3> The method for manufacturing a cured material as described in <1> or <2>, wherein the film after the heating step is a polyimide film, and the imidization rate of the film is 90% or higher. <4> The method for manufacturing a cured material as described in any one of <1> to <3>, further comprising an exposure step of selectively exposing the film between the film forming step and the heating step. <5> The method for manufacturing a cured material as described in <4> further includes a developing step between the exposure step and the heating step, wherein the exposed film is developed with a developing solution to form a pattern. <6> The method for manufacturing a cured material as described in <5>, wherein the developing solution contains an organic solvent. <7> The method for manufacturing a cured material as described in <5> or <6>, wherein the developing step is a step for forming a negative pattern. <8> The method for manufacturing a cured material as described in any one of <5> to <7>, wherein the developing solution contains an alkali. <9> The method for manufacturing a cured material as described in any one of <5> to <8> includes a processing step between the developing step and the heating step, wherein a processing solution containing an alkali is brought into contact with the pattern. <10> The method for manufacturing a cured material as described in any one of <1> to <9>, wherein the resin composition contains a photosensitizer. <11> A method for manufacturing a cured product according to any one of <1> to <10>, wherein the resin composition comprises a solvent, and the content of the precursor of the cyclized resin is 70% by mass or more relative to the total solids content of the resin composition. <12> A method for manufacturing a cured product according to any one of <1> to <11>, wherein the resin composition comprises a polymeric compound having a boiling point of 200°C or higher at 1 atmosphere. <13> A method for manufacturing a cured product according to <12>, wherein the polymeric compound having a boiling point of 200°C or higher at 1 atmosphere is a compound having three or more (meth)acrylate groups. <14> A method for manufacturing a cured product according to any one of <1> to <13>, wherein the resin composition comprises a polymeric compound having an aliphatic ring structure. <15> A method for manufacturing a hardened material as described in any one of <1> to <14>, wherein the precursor of the cyclized resin is a resin having at least one of a repeating unit represented by the following formula (2) and a repeating unit represented by formula (PAI-2).[Chemical Formula 1] In Formula (2), A1 and A2 independently represent oxygen atoms or -NRz-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and Rz represents a hydrogen atom or a monovalent organic group. In Formula (PAI-2), R117 represents a trivalent organic group, R111 represents a divalent organic group, A2 represents an oxygen atom or -NRz-, R113 represents a hydrogen atom or a monovalent organic group, and Rz represents a hydrogen atom or a monovalent organic group. <16> The method for manufacturing the hardened material as described in <15>, wherein R115 in the above formula (2) is a group represented by any one of the following formulas (X1-1) to (X1-3) or a group containing one or more aliphatic ring structures, and R117 in the above formula (PAI-2) is a group represented by any one of the following formulas (X2-1) to (X2-3) or a group containing one or more aliphatic ring structures. [Chemical Formula 2] In formula (X1-1), R represents a substituent, n1 represents an integer from 0 to 2, and * represents the bonding site with other structures. In formula (X1-2), R independently represents a substituent, m1 independently represents an integer from 0 to 3, and * represents the bonding site with other structures. In formula (X1-3), R independently represents a substituent, m1 independently represents an integer from 0 to 2, L1 represents -CRC2-, -S(=O)2-, or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures. In formula (X2-1), R represents a substituent, n2 represents an integer from 0 to 2, and * represents the bonding site with other structures. In formula (X2-2), R independently represents a substituent, m2 represents an integer from 0 to 3, m3 represents an integer from 0 to 4, and * represents the bonding site with other structures. In formula (X2-3), R independently represents a substituent, m2 represents an integer from 0 to 2, m3 represents an integer from 0 to 3, L2 represents -CRC2-, -S(=O)2-, or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures. <17> The method for manufacturing the hardened material as described in <15> or <16>, wherein R111 in formula (2) above is a group represented by any one of formulas (W1-1) to (W1-5) below or a group containing one or more aliphatic ring structures, and R111 in formula (PAI-2) above is a group represented by any one of formulas (W1-1) to (W1-3) below or a group containing one or more aliphatic ring structures. [Chemical Formula 3] In formula (W1-1), R represents a substituent, n1 represents an integer from 0 to 4, and * represents the bonding site with other structures respectively. In formula (W1-2), R independently represents a substituent, m4 independently represents an integer from 0 to 4, and * represents the bonding site with other structures respectively.In formula (W1-3), R independently represents a substituent, m4 independently represents an integer from 0 to 3, L3 represents -CRC2- or -S(=O)2-, RC represents a monovalent organic group, and * represents a bonding site with other structures. In formula (W1-4), R independently represents a substituent, n3 represents an integer from 0 to 6, and * represents a bonding site with other structures. In formula (W1-5), R independently represents a substituent, n4 independently represents an integer from 0 to 3, X1 and X2 independently represent an oxygen atom, -S(=O)2, or -CRC2-, RC independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. <18> The method for manufacturing the hardened material as described in any one of <15> to <17> satisfies at least one of the following conditions 1 and 2. Condition 1: The precursor of the above cyclized resin contains at least one repeating unit of -A2-R113 and -A1-R114 in the above formula (2), which is a group represented by the following formula (3-1). Condition 2: The precursor of the above cyclized resin contains a repeating unit of -A2-R113 in the above formula (PAI-2), which is a group represented by the following formula (3-1). [Chemical Formula 4] In formula (3-1), Z1 and Z2 independently represent organic groups, Z1 and Z2 can be bonded to form a ring structure, and * indicates a bonding site with other structures. <19> A method for manufacturing a laminate, comprising repeating the method for manufacturing a cured material described in any one of <1> to <18> a plurality of times. <20> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material described in any one of <1> to <18> or the method for manufacturing a laminate described in <19>. <21> A resin composition comprising a precursor of a cyclized resin, wherein, when the glass transition temperature is measured under the following measurement condition 1, at least one of three films of different thicknesses has a glass transition temperature of 200°C or higher. Measurement condition 1: The resin composition is coated on a silicon substrate with thicknesses of 5 μm, 10 μm, or 20 μm, respectively, dried at 100°C for 5 minutes, and then heated at 180°C for 2 hours to obtain a cured product. The glass transition temperature of the cured product cooled to 25°C is measured using a differential scanning calorimeter. <22> A cured product formed by curing the resin composition described in <21>. <23> A laminate comprising two or more layers composed of cured products formed by curing a resin composition comprising a precursor of a cyclized resin, wherein at least one of the layers composed of the cured products is a layer composed of the cured product described in <22>. <24> A semiconductor device comprising the hardened material described in <22> or the laminate described in <23>. [Effects of the Invention].

[0008] According to the present invention, a method for manufacturing a cured material that produces less gas release is provided, as well as a method for manufacturing a multilayer using the method for manufacturing the cured material and a method for manufacturing a semiconductor device. Furthermore, according to the present invention, a resin composition that produces less gas release from the obtained cured material is provided, a cured material formed by curing the resin composition, a multilayer comprising the cured material, and a semiconductor device are provided.

Implementation Method

[0009] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” refers to the range including the values ​​before and after “~” as the lower limit and upper limit, respectively. In this specification, the term “step” means not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. In the marking of groups (atomic groups) in this specification, the markings without substituted and unsubstituted include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, “alkyl” includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl). In this specification, unless otherwise specified, “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 active light or radiation. In this specification, "(meth)acrylate" refers to either "acrylate" or "methacrylate," "(meth)acrylic acid" refers to either "acrylic acid" or "methacrylic acid," and "(meth)acrylyl" refers to either "acrylyl" or "methacrylyl." In this specification, Me in the structural formula 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 components other than the solvent relative to the total mass of the composition. Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. For example, this specification uses 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 as a column to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn). Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. When THF has low solubility or is unsuitable as the eluent, NMP (N-methyl-2-pyrrolidone) can be used instead.Furthermore, unless otherwise specified, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that other layers exist above or below the reference layer among the plurality of layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Also, unless otherwise specified, the direction of the substrate stacked layers is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in this specification; in actual practice, the "upper" direction in this specification may differ from the vertical direction. In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds belonging to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferred samples is referred to as the more preferred sample.

[0010] (Method for manufacturing a cured product) The method for manufacturing a cured product of the present invention includes a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film and a heating step of heating the film at a heating temperature of 180°C or lower, wherein the glass transfer temperature of the cured product obtained is 200°C or higher.

[0011] According to the method for manufacturing a cured product of the present invention, a cured product with less gas release can be obtained. The mechanism for achieving the above-mentioned effect is not yet clear, but it is speculated to be as follows. Traditionally, a resin composition containing a precursor of a cyclized resin has been used to obtain cured products. In the method for manufacturing a cured product of the present invention, the heating temperature in the heating step is 180°C or lower, and the glass transition temperature of the film after the heating step is 200°C or higher. Here, it is speculated that when the glass transition temperature is 200°C or higher, the cyclization rate of the cyclized resin in the film is high. It is believed that because the cyclization rate is high when curing at temperatures below 180°C, the generation of gas release caused by further cyclization in the film after curing can be suppressed. It is speculated that by these effects, according to the method for manufacturing a cured product of the present invention, even a cured product obtained by heating at a low temperature of 180°C or lower can suppress the amount of gas release when the glass transition temperature is 200°C or higher.

[0012] Furthermore, it is believed that when the resin composition contains polymeric compounds, the glass transition temperature is related to the structural rigidity and reactivity of the polymeric compounds. That is, it can be said that when the glass transition temperature is above 200°C, the structure formed by the polymerization of polymeric compounds is a relatively rigid structure, and the amount of unreacted polymeric compounds in the film is small. It is believed that because the structure formed by the polymerization of polymeric compounds is a rigid structure, it is easier to suppress gas release leakage. Furthermore, it is believed that because the amount of unreacted polymeric compounds is small, the cross-linking becomes finer and denser, which is easier to suppress gas release leakage, and it is also easier to suppress the generation of gas release caused by the volatilization of the polymeric compounds themselves. Furthermore, it is believed that when the cyclization rate is high, the movement (migration) of metal ions from the metal layer to the cured material via the non-cyclized portion as the permeation path can also be suppressed. Therefore, it is speculated that when the glass transition temperature is above 200°C, the adhesion to the metal is also improved. Hereinafter, the steps included in the method for manufacturing the cured material of the present invention and the physical properties of the cured material will be described in detail.

[0013] <Film Formation Step> The method for manufacturing the cured product of the present invention includes a film formation step of applying a resin composition comprising a precursor of a cyclized resin onto a substrate to form a film. Details regarding the aforementioned resin composition will be described later.

[0014] 〔Substrate〕 The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, the substrate and metal layer formed by metal can be any of the substrates formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are even more preferred. Furthermore, a close-bonding layer, an oxide layer, etc., formed of hexamethyldisilazane (HMDS) can be provided on the surface of such substrates. Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. Regarding the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, the length of the shorter side is, for example, 100–1000 mm, preferably 200–700 mm. Furthermore, the substrate can be plate-shaped, and a panel-shaped substrate (substrate) is preferred.

[0015] Furthermore, when a resin composition is applied to the surface of the resin layer (e.g., a layer composed of a hardened material) or the surface of the metal layer to form a film, the resin layer and the metal layer become substrates.

[0016] Coating is a preferred method for applying a resin composition to a substrate.

[0017] As applicable methods, examples include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid component concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating is preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating is preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for about 10 seconds to 3 minutes. Furthermore, the method of transferring a coating formed by pre-applying it to a dummy support using the aforementioned method onto a substrate is also applicable. Regarding the transfer method, in this invention, the manufacturing methods described in Japanese Patent Application Publication No. 2006-023696, paragraphs 0023, 0036-0051, or Japanese Patent Application Publication No. 2006-047592, paragraphs 0096-0108, are also preferred. Furthermore, a step of removing excess film at the ends of the substrate can also be performed. Examples of such steps include edge bead rinse (EBR) and back-side rinse. Furthermore, a pre-wetting step can also be employed whereby, before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0018] <Drying Step> The above-mentioned film can be used in a drying step (drying step) after the film formation step (layer formation step) to remove solvent from the formed film (layer). That is, the method for manufacturing the cured product of the present invention may include a drying step for drying the film formed by the film formation step. Furthermore, it is preferable that the above-mentioned drying step is performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and further preferably 90 to 110°C. Furthermore, drying can be performed by reduced pressure. As for the drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are more preferred.

[0019] <Heating Step> The method for manufacturing the cured product of the present invention includes a heating step of heating the film at a heating temperature of 180°C or below. Here, the film in the heating step can be a film (pattern) developed after the exposure and development steps described later, or a film that has undergone the exposure step but not the development step, or a film formed by the film forming step (and, if necessary, the drying step) without undergoing other steps. Furthermore, in the method for manufacturing the cured product of the present invention, it is preferable that the film temperature is 180°C or below in all steps, including the heating step. According to the above, thermal damage to materials such as substrates can be suppressed. In the heating step, a resin such as a polyimide precursor cyclizes into a resin such as polyimide. Furthermore, during the heating step, crosslinking of unreacted crosslinking groups in the specific resin or crosslinking agent other than the specific resin described later is also performed. As for the heating temperature (maximum heating temperature) during the heating step, 20°C to 180°C is preferred, 150°C to 180°C is more preferred, and 160°C to 180°C is even more preferred. Here, it is preferable that the film after the heating step is a polyimide film. Specifically, it is preferable that the resin contained in the film after the heating step is a resin having a polyimide ring structure in the repeating unit.

[0020] The heating step is preferably a step in which the cyclization reaction of the precursor of the cyclizing resin is promoted within the membrane by heating. It is even more preferable that the cyclization reaction of the precursor of the cyclizing resin is promoted within the membrane by the action of an alkali generated from a specific resin or alkali-generating agent (described later), an alkali permeating from the developer, or an alkali permeating from the rinsing solution. That is, it is preferable that the cyclization rate of the cyclizing resin obtained from the precursor of the cyclizing resin in the membrane after the heating step increases before and after the heating step. Specifically, when the cyclization rate (%) of the precursor of the cyclizing resin in the membrane before the heating step is set as cyclization rate A, and the cyclization rate (%) of the cyclizing resin obtained from the precursor of the cyclizing resin in the membrane after the heating step is set as cyclization rate B, it is preferable that the difference in cyclization rates, expressed by the following formula, is 70% or more, more preferable that it is 80% or more, and further preferable that it is 90% or more. There is no particular upper limit to the above cyclization rate, and it can be 100%. The difference in cyclization rate = cyclization rate B - cyclization rate A. The method for determining the cyclization rate of the membrane will be explained later.

[0021] Regarding the heating step, it is preferable to perform the heating at a rate of 0.1 to 30°C / min from the initial heating temperature to the maximum heating temperature. A heating rate of 0.5 to 20°C / min is more preferable, and 2 to 10°C / min is even more preferable. By setting the heating rate to 1°C / min or more, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C / min or less, residual stress in the hardened material can be mitigated. Furthermore, in the case of an oven capable of rapid heating, a heating rate of 1 to 30°C / second from the initial heating temperature to the maximum heating temperature is preferable, 2 to 20°C / second is more preferable, and 3 to 10°C / second is even more preferable.

[0022] A starting temperature of 20–150°C is preferred, 20–130°C is more preferred, and 25–120°C is even more preferred. The starting temperature refers to the temperature at which the step of heating to the maximum heating temperature begins. For example, in the case of applying the resin composition to a substrate and then drying it, the temperature of the dried film (layer) is preferred; for example, it is preferable to start heating from a temperature 30–200°C lower than the boiling point of the solvent contained in the resin composition.

[0023] The heating time (heating time at the highest heating temperature) is preferably 30 minutes to 5 hours, and more preferably 1 hour to 3 hours. Furthermore, the temperature variation range (the difference between the maximum and minimum temperature during the heating time at the highest temperature) is preferably 0.1℃ to 20℃, more preferably 0.1℃ to 10℃, and more preferably 0.1℃ to 3℃.

[0024] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, a heating temperature of 30°C or higher is preferred, 80°C or higher is more preferred, 100°C or higher is further preferred, 120°C or higher is especially preferred, and exceeding 150°C is optimal. The upper limit of the above heating temperature is 180°C or lower, and 170°C or lower is preferred. The method for manufacturing the hardened material may include a step of heating at a heating temperature exceeding 180°C, or may not include a step of heating at a heating temperature exceeding 180°C.

[0025] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / minute and holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment simultaneously with ultraviolet irradiation. Such pretreatment steps can improve the properties of the membrane. The pretreatment step can be performed in a short time of 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 the pretreatment step can be performed in the range of 100 to 150°C, and then the second stage of the pretreatment step can be performed in the range of 150 to 180°C. Furthermore, cooling can be performed after heating, with a cooling rate of 1 to 5°C / minute being preferable.

[0026] Regarding the heating step, from the perspective of preventing the decomposition of specific resins, it is preferable to carry out the heating under reduced pressure by circulating inert gases such as nitrogen, helium, or argon, in an environment with a low oxygen concentration. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred. The heating in the heating step can be carried out under normal pressure or under reduced pressure. When heating under reduced pressure, the reduced pressure can be stopped before heating begins, during the temperature rise after heating begins, or after the maximum heating temperature is reached. There is no particular limitation on the time point at which the reduced pressure is stopped. The reduction pressure is stopped when the pressure becomes 20 mmHg (volume ratio) or less. The above pressure can be measured by a differential pressure gauge. Here, it is also preferable that the above membrane is always under reduced pressure during the time of maintaining the maximum heating temperature. There is no particular limitation on the heating method in the heating step, and examples include heating plates, infrared furnaces, electric heating ovens, hot air ovens, and infrared ovens.

[0027] <Exposure Step> The film formed after the above-described film formation step and before the above-described heating step can be used for an exposure step of selective exposure. That is, the method for manufacturing the cured material of the present invention can include an exposure step of selectively exposing the film formed by the film formation step between the above-described film formation step and the above-described heating step. Selective exposure refers to exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film. The exposure amount is not particularly limited as long as it is sufficient to cure the resin composition. For example, based on the exposure energy at a wavelength of 365 nm, 50 to 10,000 mJ / cm² is preferred, and 200 to 8,000 mJ / cm² is more preferred.

[0028] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0029] Regarding the exposure wavelength, in terms of its relationship with the light source, examples include (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), wide wavelengths (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, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. Regarding the resin composition, exposure based on high-pressure mercury lamps is preferred, among which exposure based on i rays is preferred. This results in particularly high exposure sensitivity. Furthermore, there are no particular limitations on the exposure method, as long as at least a portion of the film composed of resin components is exposed. Examples include exposure using a photomask and exposure based on direct laser imaging.

[0030] <Post-exposure heating step> The above-described film can be used in a post-exposure heating step. That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. It is preferable that the cyclization rate of the film after the heating step (i.e., the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) does not substantially increase before and after the post-exposure heating step. Specifically, it is preferable that the difference in the cyclization rate is 30% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the cyclization rate is not particularly limited and can be 0%. In particular, when the above-described film does not contain the photoalkali generating agent described later, it is preferable that the difference in the cyclization rate is 30% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the cyclization rate is not particularly limited and can be 0%. 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 more preferably 60℃~120℃. The heating time in the post-exposure heating step is preferably 30 seconds~300 minutes, and more preferably 1 minute~10 minutes. Regarding the heating rate in the post-exposure heating step, it is preferably 1~12℃ / min from the initial heating temperature to the maximum heating temperature, more preferably 2~10℃ / min, and further preferably 3~10℃ / min. Furthermore, the heating rate can be appropriately adjusted during the heating process. There are no particular limitations on the heating method in the post-exposure heating step; known heating plates, ovens, infrared heaters, etc., can be used. Also, it is preferable to conduct the heating in a low-oxygen concentration environment by circulating inert gases such as nitrogen, helium, or argon.

[0031] <Developing Step> The exposed film can be used in a developing step to form a pattern by developing with a developing solution. That is, the method for manufacturing the cured material of the present invention may include a developing step to form a pattern by developing the film exposed by the exposure step with a developing solution. By developing, one of the exposed and unexposed portions of the film is removed, forming a pattern. Here, the development in which the unexposed portion of the film is removed by the developing step is called negative development, and the resulting pattern is called a negative pattern. Similarly, the development in which the exposed portion of the film is removed by the developing step is called positive development, and the resulting pattern is called a positive pattern. In the present invention, it is preferable that the developing step is the step of forming a negative pattern.

[0032] 〔Developer solution〕 As the developer solution used in the developing step, examples include alkaline aqueous solutions or developer solutions containing organic solvents, with developer solutions containing organic solvents being more preferred.

[0033] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is also mentioned. For example, when using TMAH, it is preferable that the content of alkaline compounds in the developer is 0.01 to 10% by mass of the total amount of developer, even better that it is 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass.

[0034] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g.: Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably including diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone 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... Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of sulfides include, for example, dimethyl sulfide; examples of alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl methamide.

[0035] Furthermore, when the developer contains an organic solvent, one type of organic solvent or two or more types of organic solvent may be used. In this invention, it is particularly preferred that the developer contains at least one type 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 type selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and it is most preferably a developer containing cyclopentanone.

[0036] When the developer contains organic solvents, it is preferable that the organic solvent content relative to the total mass of the developer is 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 also be 100% by mass. Also, when the developer contains organic solvents, it is preferable that the water content relative to the total mass of the developer is 10% by mass or more, more preferably 5% by mass or more, further preferably 1% by mass or more, and especially preferably 0.1% by mass or more. The above water content is not particularly limited and can be 0% by mass.

[0037] It is also preferable that the developer contains at least one compound selected from the group consisting of alkali and alkali-generating agents. According to the above-described sample, in the developing step, the alkali or alkali-generating agent in the developer permeates into the membrane, and in the subsequent heating step, the cyclization of the cyclizing resin precursor is promoted by the action of the alkali generated from the alkali or alkali-generating agent. As a result, it is believed that the cyclization rate of the cyclizing resin obtained from the cyclizing resin precursor in the membrane after the heating step increases, and even when heated at a low temperature below 180°C, the glass transition temperature increases and less gas release is generated. In the above-described sample, from the viewpoint of suppressing the amount of gas release, it is preferable that the developer contains an alkali. Furthermore, in the above-described sample, it is preferable that the developer contains an organic solvent.

[0038] -Base- From the viewpoint of reliability when remaining in the hardened material (adhesion to the substrate when the hardened material is further heated), organic bases are preferred. Furthermore, as a base, a base having an amino group is preferred; primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides are preferred. To promote amide imidization, primary amines, secondary amines, and tertiary amines are preferred, with secondary or tertiary amines being more preferred, and tertiary amines being the best. From the viewpoint of the mechanical properties (elongation at break) of the hardened material, a base that is not easily retained in the obtained hardened material is preferred. From the viewpoint of promoting cyclization (amide imidization), a base that is not easily reduced by volatilization or vaporization before heating is preferred. Therefore, a boiling point of 30°C to 350°C at atmospheric pressure (101, 325 Pa) is preferred, 80°C to 270°C is more preferred, and 100°C to 230°C is further preferred. Furthermore, it is preferable that the boiling point of the alkali is higher than the boiling point of the organic solvent contained in the developer by subtracting 20°C, and even more preferable that it is higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100°C, it is preferable that the boiling point of the alkali used is 80°C or higher, and even more preferable that it is 100°C or higher.

[0039] It is preferable that the pKa of the conjugate acid of the above-mentioned base in DMSO (dimethyl sulfoxide) is 1 or higher, and more preferably 3 or higher. There is no particular upper limit to the above-mentioned pKa, but it is preferable that it is 20 or lower. When the conjugate acid of the above-mentioned base has multiple pKas in DMSO, it is preferable that at least one of them is within the above-mentioned range. Here, the above-mentioned pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the values ​​can be referred to in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; ed.: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the pKa will be calculated from the structural formula using software such as ACD / pKa (made by ACD / Labs).

[0040] Specific examples of alkalis contained in the developer include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, dimethylcyclohexylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diacrylbicycloundecene), DABCO (1,4-diacrylbicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N- Methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexyl, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylamine ethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, etc.

[0041] When the developer contains alkali, the alkali content relative to the total mass of the developer is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and further preferably 0.5 to 20% by mass. Furthermore, when the alkali is not liquid at 10 to 30°C, the alkali content is preferably 0.3 to 30% by mass, and more preferably 0.5 to 20% by mass. One type of alkali may be used alone, or two or more types may be used simultaneously. When two or more types of alkali are used simultaneously in the developer, their total content within the above-mentioned range is preferred.

[0042] - Alkali generating agent - The developer may contain an alkali generating agent. Examples of alkali generating agents include photoalkali generating agents or thermal alkali generating agents, with thermal alkali generating agents being preferred. For example, the alkali generating agent described as a component included in the resin composition described below can be used without particular limitation as the aforementioned photoalkali generating agent or thermal alkali generating agent.

[0043] When the developer contains an alkali-generating agent, the content of the alkali-generating agent relative to the total mass of the developer is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and further preferably 0.08 to 5% by mass. One type of alkali-generating agent may be used alone, or two or more types may be used simultaneously. When two or more alkali-generating agents are used simultaneously in the developer, their total content within the above-mentioned range is preferred.

[0044] The developer may further contain other components. Examples of other components include, for instance, known surfactants and known defoamers.

[0045] [Developer Supply Method] The developer supply method is not particularly limited as long as the desired pattern can be formed. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous development. The type of nozzle is not particularly limited; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles. From the viewpoints of developer penetration, removal of non-image areas, and manufacturing efficiency, the method of supplying the developer using a direct-flow nozzle or the method of continuous supply using a spray nozzle is preferable. From the viewpoint of developer penetration into the image area, the method of supplying using a spray nozzle is more preferable. Alternatively, the following steps can be used: after continuously supplying the developer using a direct-flow nozzle, rotating the substrate to remove the developer from the substrate; after drying by rotation, continuously supplying the developer again using a direct-flow nozzle; and rotating the substrate to remove the developer from the substrate. This step can also 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, maintaining the developer on the substrate in a substantially static state, vibrating the developer on the substrate using ultrasound or the like, and combining these methods are possible.

[0046] The preferred development time is 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular limitation on the temperature of the developer during development, but it is preferred to be carried out at 10 to 45°C, and more preferably at 18 to 30°C.

[0047] <Processing Steps> The method for manufacturing the cured product of the present invention preferably includes a processing step between the developing step and the heating step, in which a processing liquid containing at least one compound selected from the group consisting of alkali and alkali-generating agents is brought into contact with the pattern. More preferably, the method includes a processing step between the developing step and the heating step, in which a processing liquid containing alkali is brought into contact with the pattern. It is believed that, according to this approach, at least one compound selected from the group consisting of alkali and alkali-generating agents contained in the processing liquid permeates into the pattern after developing. As a result, it is believed that the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step increases, and even when heated at a low temperature below 180°C, the glass transfer temperature increases, resulting in a cured product with less gas release.

[0048] The above-mentioned processing step is preferably a rinsing step of cleaning the above-mentioned pattern with the above-mentioned processing solution. Furthermore, it is preferable that the processing solution is a rinsing solution. Moreover, it is preferable that the above-mentioned processing solution is a rinsing solution and the above-mentioned processing step is a rinsing step of cleaning the pattern with the above-mentioned rinsing solution. That is, it is preferable that the above-mentioned processing step is a rinsing step of cleaning the above-mentioned pattern (the pattern obtained by the developing step) with a rinsing solution containing at least one compound selected from the group including alkali and alkali generating agents. Furthermore, the above-mentioned processing step may be performed, for example, after the "other rinsing steps" described later.

[0049] [Processing liquid] The water content relative to the total mass of the processing liquid is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and especially preferably 2% by mass or less. The lower limit of the above water content is not particularly limited and can be 0% by mass.

[0050] As a processing liquid, for example, it is possible to use a solvent contained in the developer and a solvent different from the solvent contained in the developer (e.g., an organic solvent different from the organic solvent contained in the developer) and a solvent containing at least one compound selected from the group including alkali and alkali generating agents.

[0051] -Base- The preferred form of the base contained in the treatment solution is the same as the preferred form of the base contained in the developing solution described above. Among them, a tertiary amine is preferred as the base contained in the treatment solution. Furthermore, it is preferred that the base contained in the treatment solution does not readily react with the solvent used in the treatment solution (e.g., cyclopentanone, etc.).

[0052] When the treatment solution contains alkali, the alkali content relative to the total mass of the treatment solution is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and further preferably 0.5 to 20% by mass. Furthermore, when the alkali is not liquid at 10 to 30°C, the alkali content is preferably 0.3 to 30% by mass, and more preferably 0.5 to 20% by mass. One type of alkali may be used alone, or two or more types may be used simultaneously. When two or more types of alkali are used simultaneously in the treatment solution, their total content within the above-mentioned range is preferred.

[0053] -Alkali generating agent- The treatment solution may contain an alkali generating agent. Examples of alkali generating agents include light-induced alkali generating agents or heat-induced alkali generating agents, with heat-induced alkali generating agents being preferred. For example, light-induced alkali generating agents or heat-induced alkali generating agents described as components included in the resin composition described later can be used without particular limitation.

[0054] When the treatment solution contains an alkali-generating agent, the content of the alkali-generating agent relative to the total mass of the treatment solution is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and further preferably 0.08 to 5% by mass. One type of alkali-generating agent may be used alone, or two or more may be used simultaneously. When two or more alkali-generating agents are used simultaneously in the treatment solution, their total content within the above-mentioned range is preferred.

[0055] As an organic solvent contained in the treatment liquid, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., 3-alkoxy... Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate) Esters, such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, such as preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone 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 Examples of suitable bases include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene; sulfoxides include, for example, dimethyl sulfoxide; alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc.; and amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. Furthermore, when the above-mentioned bases (e.g., organic bases) are liquids in the environment of the treatment liquid, they can be used as both solvents and bases.

[0056] Furthermore, when the treatment solution contains an organic solvent, one type of organic solvent or two or more types of organic solvent can be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

[0057] When the treatment solution contains an organic solvent, it is preferable that 50% or more by mass of the organic solvent is present relative to the total mass of the treatment solution, more preferably 70% or more by mass of the organic solvent, and even more preferably 90% or more by mass of the organic solvent. Furthermore, 100% by mass of the treatment solution may be an organic solvent.

[0058] The treatment liquid may further contain other components. Examples of other components include, for example, known surfactants and known defoamers.

[0059] [Method for supplying the processing liquid] There are no particular limitations on the method for supplying the processing liquid, as long as it allows the processing liquid to come into contact with the pattern obtained in the developing step. For example, the processing liquid can be supplied onto the pattern obtained in the developing step. There are no particular limitations on the above-mentioned supply method; methods include immersing the substrate in the processing liquid, supplying the processing liquid to the substrate by immersion in a spin coat, supplying the processing liquid by spraying it onto the substrate, and continuously supplying the processing liquid to the substrate using a mechanism such as a direct current nozzle. From the viewpoint of the permeability of the processing liquid to the image section and manufacturing efficiency, methods for supplying the processing liquid using spray nozzles, direct current nozzles, or atomizing nozzles are preferred. Continuous supply using a nozzle is preferable. From the viewpoint of the permeability of the processing liquid to the image section, maintaining the processing liquid supplied by the nozzle on the substrate is even better. The above-mentioned methods for supplying the processing liquid (e.g., combinations of immersion-based supply and spray-based supply, and immersion-based supply and direct current nozzle supply) can be used simultaneously. For example, the swirling immersion method facilitates the penetration of the post-treatment solution after membrane swelling. Furthermore, the treatment solution is sufficient to be used in at least one of the simultaneously used methods. In this invention, it is also possible to provide a treatment solution that does not contain alkali or alkali-generating agents (e.g., the rinsing solution in other rinsing steps described later) onto the pattern (e.g., after rinsing the pattern with rinsing solution in other rinsing steps described later), and then perform the treatment step using the treatment solution. The preferred form of the treatment solution that does not contain alkali or alkali-generating agents is the same as the preferred form of the rinsing solution in other rinsing steps described later. The method for supplying the treatment solution that does not contain alkali or alkali-generating agents to the pattern in the above-described form is not particularly limited; a swirling immersion method can be cited as an example. The method for supplying the treatment solution to the pattern in the above-described form is not particularly limited; a spray method or a direct-flow nozzle method can be cited as preferred examples. It is believed that by supplying the alkali-free treatment solution through swirling immersion, at least one compound selected from the group consisting of alkalis and alkali-generating agents in the treatment solution supplied after pattern swelling can easily penetrate into the pattern, making it easier to obtain effects such as increased elongation at break. Furthermore, by supplying the treatment solution through spraying, direct-flow nozzles, etc., the removal (rinsing) of developing residues may also be excellent. Moreover, as a method for supplying the treatment solution in the processing step, steps such as continuously supplying the treatment solution to the substrate, maintaining the treatment solution on the substrate in a substantially static state, vibrating the treatment solution on the substrate using ultrasound, etc., and combinations thereof can be employed. Among these, the processing step of supplying the treatment solution through spraying or continuously supplying it to the developed pattern is preferred. Furthermore, it is also preferred that the developing step in the developing step is performed by swirling immersion developing, and that the supply of the treatment solution in the processing step is performed at least once by spraying or continuous supplying it through direct-flow nozzles, etc.Based on the above-mentioned state, by immersing the developed pattern in a rotary immersion solution to induce swelling, at least one compound selected from the group consisting of alkali and alkali-generating agents in the treatment solution can easily penetrate into the pattern, thereby making it easier to obtain effects such as increased elongation at break.

[0060] The processing time in the processing step (i.e., the time during which the processing liquid comes into contact with the above pattern) is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the processing liquid in the processing step is not particularly limited, but it is preferably carried out at 10 to 45°C, and more preferably at 18°C ​​to 30°C.

[0061] <Other Rinsing Steps> The method for manufacturing the cured product of the present invention may include a rinsing step (hereinafter also referred to as "other rinsing steps") of rinsing the pattern (the pattern obtained by the developing step) with a rinsing solution that does not contain either alkali or alkali-generating agent. The method for manufacturing the cured product of the present invention may include other rinsing steps, for example, before the aforementioned processing step and after the aforementioned developing step. Furthermore, when the method for manufacturing the cured product of the present invention does not include the aforementioned processing step, other rinsing steps may be included after the aforementioned developing step and before the aforementioned heating step. As the rinsing solution in the other rinsing steps, the same liquid as the aforementioned processing solution can be used, except that it does not contain alkali or alkali-generating agent. The preferred state of each component contained in the rinsing solution is the same as the preferred state of each component other than alkali and alkali-generating agent contained in the aforementioned processing solution. Furthermore, the rinsing solution can be supplied to the pattern by the same method as the aforementioned processing solution.

[0062] <Post-development exposure step> The pattern obtained by the development step (or the washed pattern in the case of a washing step) can be used instead of the heating step described above, or in addition to the heating step described above, for exposing the pattern after the development step in a post-development exposure step. That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step. In the post-development exposure step, for example, a cyclization reaction of polyimide precursors, etc., can be promoted by photosensitive alkali generating agent, or a reaction of decomposing acidic groups by photosensitive acid generating agent. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for all of the above-mentioned pattern to be exposed. Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure step is preferably 50–20,000 mJ / cm², and more preferably 100–15,000 mJ / cm². Regarding the post-development exposure step, the light source used in the above-mentioned exposure step can be used, and broadband light is preferred.

[0063] <Metal Layer Forming Step> A metal layer forming step in which the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step) can be used to form a metal layer on the pattern. That is, the method for manufacturing the cured material of the present invention preferably includes a metal layer forming step in which a metal layer is formed on the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step).

[0064] As a metal layer, there is no particular limitation, and existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing such metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0065] The method for forming the metal layer is not particularly limited, 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 deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining the above 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 plating solution and copper cyanide plating solution can be cited.

[0066] As for the thickness of the metal layer, 0.01 to 50 μm is preferred, and 1 to 10 μm is even more preferred, based on the thickest part.

[0067] <Physical Properties of the Cured Material> [Glass Transition Temperature] In the method for manufacturing the cured material of the present invention, the glass transition temperature of the obtained cured material is preferably 200°C or higher, 220°C or higher, and more preferably 250°C or higher. There is no particular upper limit to the above-mentioned glass transition temperature, but 350°C or lower is preferred. The above-mentioned glass transition temperature is calculated by the method described in the examples.

[0068] [Cycloning Rate] In the method for manufacturing the cured product of the present invention, it is preferable that the cyclization rate of the cyclized resin obtained from the cyclized resin precursor in the film after the heating step is 90% or more, more preferably 95% or more, further preferably 98% or more, and especially preferably 99% or more. In particular, it is preferable that the film after the heating step is a polyimide film and that the cycloimidization rate of the polyimide is 90% or more, more preferably 95% or more, further preferably 98% or more, and especially preferably 99% or more. The upper limit of the above cyclization rate is not particularly limited and can be 100%. The above cyclization rate is calculated by the following method. When the precursor of the cyclized resin is a polyimide precursor or a polyamide-cycloimide precursor, the infrared absorption spectrum of the film after the heating step is measured, and the peak intensity P1 of the absorption peak originating from the cycloimide structure, i.e., around 1377 cm⁻¹, is determined. Next, after heat treatment at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 near 1377 cm⁻¹ was determined. Using the obtained peak intensities P1 and P2, the cyclization rate (nimidization rate) can be calculated according to the following formula: Nimidization rate (%) = (peak intensity P1 / peak intensity P2) × 100. When the precursor of the cyclized resin is a polybenzoxazole precursor, the absorption peak of the nimidyl structure of the membrane after the above heating step, i.e., the peak intensity Q1 near 1650 cm⁻¹, was determined. Then, the absorption intensity of the aromatic ring observed near 1490 cm⁻¹ was normalized. Next, after heat treatment at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 near 1650 cm⁻¹ was determined, and normalized using the absorption intensity of the aromatic ring observed near 1490 cm⁻¹. The cyclization rate (oxazolization rate) can be calculated using the obtained peak intensity specifications Q1 and Q2 according to the following formula: Oxazolization rate (%) = (specification value of peak intensity Q1 / specification value of peak intensity Q2) × 100. Furthermore, in the above determination of cyclization rate (oxazolization rate), if the composition contains a compound that absorbs at wavelengths of 1377 cm⁻¹, 1490 cm⁻¹, or 1650 cm⁻¹ (e.g., phthalimide), the peak intensity originating from that compound can be excluded as background.

[0069] [Form, etc.] The form of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured composition is preferably film-shaped. Furthermore, by pattern processing of the resin composition, the shape of the cured composition can also be selected according to applications such as forming a protective film on the wall surface, forming conductive through holes, adjusting impedance, electrostatic capacitance or internal stress, and imparting heat dissipation function. The thickness of the cured composition (the film composed of the cured composition) is preferably 0.5 μm or more and 150 μm or less. Furthermore, the shrinkage rate of the film before and after the heating step is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume before and after the heating step, which can be calculated according to the following formula: Shrinkage rate [%] = 100 - (volume after heating step ÷ volume before heating step) × 100

[0070] It is preferable that the elongation at break of the hardened material is 30% or more, more preferably 40% or more, and even more preferably 50% or more. There is no particular upper limit to the above-mentioned elongation at break; for example, 200% or less is acceptable. The elongation at break can be measured in accordance with JIS (Japanese Industrial Standards) K 6251:2017. Furthermore, it is preferable that the coefficient of thermal expansion (CTE) of the hardened material is 70 ppm / K or less, more preferably 60 ppm / K or less, and even more preferably 50 ppm / K or less. There is no particular lower limit to the above-mentioned CTE; it can be 0 ppm / K.

[0071] <Applications> Examples of applications applicable to the manufacturing method of the cured material of the present invention or the cured material of the present invention include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress-relief films, etc. Other examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used for practical mounting purposes, such as those described above. For these applications, references can be made to 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, etc.

[0072] Furthermore, the method for manufacturing 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, the use of forming parts in etching, and the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0073] (Resin composition) Hereinafter, the resin composition used in the method for manufacturing the cured product of the present invention will be described.

[0074] <Specific Resin> The resin composition of the present invention includes a precursor of a cyclized resin (specific resin). It is preferable that the cyclized resin contains an imine ring structure or an oxazole ring structure in its main chain structure. In the present invention, the main chain refers to the longest bonded chain in the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide. The precursor of the cyclized resin refers to a resin whose chemical structure changes due to external stimuli to become a cyclized resin; it is preferable that the chemical structure changes due to heat to become a cyclized resin; and it is even more preferable that the resin becomes a cyclized resin by forming a ring structure through a heat-induced ring-closing reaction. Examples of cyclized resin precursors include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. That is, the resin composition of the present invention preferably includes at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors as the specific resin. It is preferable that the resin composition of the present invention includes a polyimide precursor as the specific resin. Furthermore, it is preferable that the specific resin has polymerizable groups, and it is even more preferable that it includes free radical polymerizable groups. When the specific 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. The sensitizer described later can be further included as needed. For example, a negative photosensitive film can be formed from such resin compositions of the present invention. Furthermore, the specific resin may have polar conversion groups such as acid-decomposing groups. When the specific resin has acid-decomposing groups, it is preferable that the resin composition of the present invention includes the photoacid generator described later. For example, such resin compositions of the present invention can be used to form chemically amplified positive or negative photosensitive films.

[0075] Here, it is preferable that the precursor of the cyclized resin is a resin having at least one of the repeating units represented by formula (2) described later and the repeating units represented by formula (PAI-2). In the above-described state sample, from the viewpoint of suppressing the release of gas from the cured material, it is preferable that R115 in formula (2) is a group represented by any one of formulas (X1-1) to (X1-3) or a group containing one or more aliphatic ring structures, and that R117 in formula (PAI-2) is a group represented by any one of formulas (X2-1) to (X2-3) or a group containing one or more aliphatic ring structures. Hereinafter, such a state sample will be described as state sample A. Furthermore, in the above-described state A, from the viewpoint of suppressing the release of gas from the hardened material, it is preferable that R111 in the following formula (2) is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group containing one or more aliphatic ring structures, and that R111 in the following formula (PAI-2) is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group containing one or more aliphatic ring structures. Moreover, in the above-described state A, from the viewpoint of suppressing the release of gas from the hardened material, it is preferable that at least one of the following conditions 1 and 2 is satisfied. Condition 1: The precursor of the cyclized resin contains at least one repeating unit of -A2-R113 and -A1-R114 in the above formula (2) that is a group represented by the following formula (3-1). Condition 2: The precursor of the cyclized resin contains a repeating unit of -A2-R113 in the above formula (PAI-2), which is represented by the group in the following formula (3-1). The precursor of the cyclized resin satisfies Condition 1 when it does not contain a repeating unit represented by formula (PAI-2), and satisfies Condition 2 when it does not contain a repeating unit represented by formula (2). It is more preferable that the precursor of the cyclized resin satisfies at least one of Condition 1 and Condition 2 when it contains a repeating unit represented by formula (2) and a repeating unit represented by formula (PAI-2).

[0076] 〔Polyimine Precursor〕 The type of polyimine precursor used in this invention is not particularly limited, 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 -NRz-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and Rz represents a hydrogen atom or a monovalent organic group.

[0077] In formula (2), A1 and A2 independently represent oxygen atoms or -NHZ-, with oxygen atoms being preferred. Rz represents hydrogen atoms or monovalent organic groups, with hydrogen atoms being preferred. When Rz represents a monovalent organic group, the preferred state of RZ is the same as the preferred state of Z1 in formula (3-1) described later. R111 in formula (2) represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups. 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 groups composed of combinations thereof are preferred. Groups containing aromatic groups with 6 to 20 carbon atoms are even more preferred. The hydrocarbon groups in the chain of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups in the ring members of the aforementioned cyclic aliphatic and aromatic groups can be replaced by groups containing heteroatoms. As a preferred embodiment of the invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, with a particular emphasis on groups represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. These preferred ranges are as described above.

[0078] R111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include straight-chain or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, diamines containing a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof, are preferred; diamines containing an aromatic group with 6 to 20 carbon atoms are even more preferred. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group in the ring members of the aforementioned cyclic aliphatic and aromatic groups can be replaced by a group containing a heteroatom. Examples of groups containing aromatic groups include the following groups.

[0079] [Chemical Formula 6] In the formula, A represents a single bond or a divalent linker. A single bond or a group selected from aliphatic hydrocarbons with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof is preferred. A single bond, a group selected from alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2- is even more preferred. -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2- is further preferred. * In the formula, * indicates a bonding site with other structures.

[0080] As a diamine, specifically examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4'- or 3,3'- -Diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, Bis(3-amino-4-hydroxyphenyl) guanidine, bis(4-amino-3-hydroxyphenyl) guanidine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] guanidine, bis[4-(3-aminophenoxy)phenyl] guanidine, bis[4-(2-aminophenoxy)phenyl] guanidine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl guanidine, 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- and 2,5-diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminophen, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotriphenylamine Fluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-fluoropropane [-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl benzoyl, 4, At least one diamine selected from the following: 4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl benzoxane, 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.

[0081] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0082] Alternatively, the diamine having two or more alkyl diol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0083] From the viewpoint of the flexibility of the obtained organic membrane, R111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO2-, 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, or a group consisting of -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably alkyl.

[0084] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R111 is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is even more preferable that the divalent organic group represented by formula (61) is preferred. Formula (51) [Chemical Formula 7] In formula (51), R50 to R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R50 to R57 is a fluorine atom, a methyl group, or a trifluoromethyl group. *Independently represents the bonding site with the nitrogen atom in formula (2). Examples of monovalent organic groups of R50 to R57 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), R58 and R59 are independently fluorine atoms, methyl groups, or trifluoromethyl groups, respectively, and * independently represent bonding sites with nitrogen atoms in formula (2). Examples of diamines that impart the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0085] Furthermore, from the viewpoint of suppressing gas release from the cured product, it is preferable that R111 is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group containing one or more aliphatic ring structures. It is believed that by including such a structure in R111, the glass transfer temperature of the cured product increases, thereby suppressing gas release from the cured product. [Chemical Formula 9] In formula (W1-1), R represents a substituent, n1 represents an integer from 0 to 4, and * represents the bonding site with other structures. In formula (W1-2), R independently represents a substituent, m4 independently represents an integer from 0 to 4, and * represents the bonding site with other structures. In formula (W1-3), R independently represents a substituent, m4 independently represents an integer from 0 to 3, L3 represents -CRC2- or -S(=O)2-, RC represents a monovalent organic group, and * represents the bonding site with other structures. In formulas (W1-4), R independently represents a substituent, n3 represents an integer from 0 to 6, and * represents a bonding site with other structures. In formulas (W1-5), R independently represents a substituent, n4 independently represents an integer from 0 to 3, X1 and X2 independently represent an oxygen atom, -S(=O)2- or -CRC2-, RC independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. Furthermore, in this specification, when a bond is written in a chemical formula as crossing the edge of a ring structure, it indicates that the bond can be bonded to any ring member within the ring structure. Also, when a bond is written in a chemical formula as crossing the edges of multiple ring structures, it indicates that the bond can be bonded to any ring member within the multiple ring structures.

[0086] In formula (W1-1), the substituent represented by R is not particularly limited, and examples include aliphatic hydrocarbon groups, aryl groups, alkoxy groups, alkyl carbonyl groups, alkoxy carbonyl groups, alkyl carbonyloxy groups, aryloxy groups, aryl carbonyl groups, aryl carbonyloxy groups, halogen atoms, etc. As the aforementioned aliphatic hydrocarbon group, alkyl groups are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 4 carbon atoms are even more preferred. As the aforementioned aryl group, aromatic hydrocarbon groups are preferred, and phenyl groups are more preferred. As the aforementioned alkoxy, alkyl carbonyl, alkoxy carbonyl, and alkyl carbonyloxy groups, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred. The aforementioned alkyl groups may be further substituted with halogen atoms, etc. Examples of such substitutions include trifluoromethyl and pentafluoromethyl. As the aforementioned aryloxy, aryl carbonyl, aryloxy carbonyl, and aryl carbonyloxy groups, aryl hydrocarbon groups having aromatic hydrocarbon groups is preferred, and phenyl groups are more preferred. In equation (W1-1), n1 being an integer from 0 to 3 is preferred, and 0 or 1 is even better. In equation (W1-2), the preferred states of R and m4 are the same as those of R and n1 in equation (W1-1), respectively. In equation (W1-3), the preferred state of R is the same as that of R in equation (W1-1). In equation (W1-3), m4 being an integer from 0 to 2 is preferred, and 0 or 1 is even better. In equation (W1-3), L3 represents -CRC2- or -S(=O)2-, with -S(=O)2- being preferred. In equation (W1-3), the preferred state of RC is the same as that of R in equation (W1-1). In equation (W1-4), the preferred state of R is the same as that of R in equation (W1-1). In formula (W1-4), it is preferable for n3 to be an integer from 0 to 4, and even more preferable for n3 to be an integer from 0 to 2. In formula (W1-5), the preferred state of R is the same as that of R in formula (W1-1). In formula (W1-5), it is preferable for n4 to be an integer from 0 to 2 independently, and even more preferable for n4 to be 0 or 1. In formula (W1-5), it is preferable for X1 and X2 to be either an oxygen atom or -S(=O)2-, and for X2 to be -CRC2-. In formula (W1-5), it is preferable for RC to be either a hydrogen atom or a hydrocarbon group, and even more preferable for RC to be a hydrogen atom.

[0087] As a group comprising one or more aliphatic ring structures, examples include groups consisting of one aliphatic ring structure or groups consisting of two or more aliphatic ring structures linked by single bonds, -O-, or -C(=O)- bonds. The aliphatic ring structure in a group comprising one or more aliphatic ring structures can be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure. Furthermore, the aliphatic ring structure can be a heterocyclic structure, but an aliphatic hydrocarbon ring structure is preferred. Also, the aliphatic ring structure in a group comprising one or more aliphatic ring structures can be a monocyclic ring, or a condensation ring, a cross-linked condensation ring, a spirocyclic ring, or other heterocyclic rings. Examples of aliphatic ring structures in a group comprising one or more aliphatic ring structures include cyclohexane structures, cyclohexene structures, and bicyclic [2.2.2]octyl-5-ene structures.

[0088] Specific examples of groups formed by any one of formulas (W1-1) to (W1-5) or groups comprising one or more aliphatic ring structures include the following structures, but are not limited thereto. In the following structures, * indicates a bond site with other structures. [Chemical Formula 10]

[0089] In formula (2), R115 represents a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures. [Chemical Formula 11] In Formula (5), R112 is a single bond or a divalent group. It is preferred that the single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof. It is even more preferred that the single bond or a group selected from alkyl groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2- is selected. It is even more preferred that the divalent group is selected from the group including -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0090] Furthermore, from the viewpoint of suppressing the release of gas from the hardened material, it is preferable that R115 is a group represented by any one of the following formulas (X1-1) to (X1-3) or a group containing one or more aliphatic ring structures. [Chemical Formula 12] In formula (X1-1), R represents a substituent, n1 represents an integer from 0 to 2, and * represents the bonding site with other structures. In formula (X1-2), R independently represents a substituent, m1 independently represents an integer from 0 to 3, and * represents the bonding site with other structures. In formula (X1-3), R independently represents a substituent, m1 independently represents an integer from 0 to 3, L1 represents -CRC2-, -S(=O)2- or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures.

[0091] In formula (X1-1), the preferred state of R is the same as the preferred state of R in formula (W1-1) above. In formula (X1-1), n1 represents 0 or 1 as preferred. In formula (X1-2), the preferred state of R is the same as the preferred state of R in formula (W1-1) above. In formula (X1-2), m1 is 0 or 1 as preferred. In formula (X1-3), the preferred state of R is the same as the preferred state of R in formula (W1-1). In formula (X1-3), m1 is 0 or 1 as preferred. In formula (X1-3), L1 represents -CRC2-, -S(=O)2-, or -O-, with -S(=O)2- being preferred. In formula (X1-3), the preferred state of RC is the same as the preferred state of R in formula (W1-1).

[0092] The preferred state of the aliphatic ring structure in the group comprising one or more aliphatic ring structures is the same as the preferred state of the aliphatic ring structure in the group comprising one or more aliphatic ring structures in R111 above.

[0093] Specific examples of groups formed by any one of the formulas (X1-1) to (X1-3) or groups comprising one or more aliphatic ring structures include the following structures, but are not limited thereto. In the following structures, * indicates a bond site with other structures. [Chemical Formula 13]

[0094] Specifically, R115 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As a structure belonging to R115, the polyimide precursor may contain only one tetracarboxylic acid dianhydride residue, or it may contain two or more. It is preferred that the tetracarboxylic acid dianhydride is represented by the following formula (O). [Chemical Formula 14] In formula (O), R115 represents a tetravalent organic group. R115 has the same meaning as R115 in formula (2), and the preferred range is also the same.

[0095] Specific examples of tetracarboxylic dianhydrides include pyrocalcite 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 dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0096] Furthermore, as a better example, one can also cite the tetracarboxylic acid dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0097] In formula (2), at least one of R111 and R115 may have an OH group. More specifically, as R111, residues of diaminophenol derivatives may be cited.

[0098] In formula (2), R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to include 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 R113 and R114 contains a polymerizable group, and it is even more preferable that both contain polymerizable groups. It is also preferable that at least one of R113 and R114 contains two or more polymerizable groups. As a polymerizable group, it is a group capable of cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxybutyl, benzoxazole, terminal 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 groups represented by formula (III) below being preferred.

[0099] [Chemical Formula 15]

[0100] In formula (III), R200 represents a hydrogen atom, methyl, ethyl, or hydroxymethyl, with a hydrogen atom or methyl being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R201 represents an alkyl group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, an cycloalkyl group, or a polyalkylene group. Preferred examples of R201 include alkyl groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene groups. Vinyl, propenyl, and other propenyl groups, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene groups are more preferred, and vinyl, propenyl, and other propenyl groups or polyalkylene groups are even more preferred. In this invention, a polyalkylene group refers to a group with two or more propenylene groups directly bonded together. The alkyl groups in the plurality of alkyl groups contained in the polyalkylene group can be the same or different. When the polyalkylene group contains a plurality of alkyl groups with different alkyl groups, the arrangement of the alkyl groups in the polyalkylene group can be random, block-shaped, or alternating. It is preferred that the number of carbon atoms in the alkyl group (including the number of carbon atoms of the substituent when the alkyl group has substituents) is 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkyl group can have substituents. Examples of preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, it is preferred that the number of alkyl groups contained in the polyalkylene group (the number of repetitions of the polyalkylene group) is 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups are preferred as polyvinyloxy groups, with polyvinyloxy or polypropyleneoxy being more preferred, and polyvinyloxy being even more preferred. Among the aforementioned groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the number of repetitions of the ethyleneoxy groups, etc., in these groups is as described above.

[0101] In formula (2), when R113 is a hydrogen atom or R114 is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an ethylene unsaturated bond. As an example of such a tertiary amine compound having an ethylene unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

[0102] In formula (2), at least one of R113 and R114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes by the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal, ketal, silicone, silicone ether, and tertiary alkyl ester are preferred. From the viewpoint of exposure sensitivity, acetal or ketal is more preferred. Specific examples of acid-degradable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tertiary butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is more preferred.

[0103] Furthermore, from the viewpoint of suppressing the release of gas from the hardened material, it is also preferable to include repeating units containing at least one of -A2-R113 and -A1-R114 that are groups represented by the following formula (3-1). [Chemical Formula 16] In formula (3-1), Z1 and Z2 independently represent organic groups, Z1 and Z2 can be bonded to form a ring structure, and * indicates the bonding site with other structures.

[0104] It is believed that, based on this type of state, when a specific resin undergoes ring closure, an alkali is generated from the structure represented by formula (3-1) and further promotes ring closure. Therefore, even for cured products obtained by heating at a low temperature below 180°C, the glass transition temperature will increase, resulting in cured products with less gas release. Furthermore, for example, when using the alkali-generating agent described later, sometimes residues from the alkali-generating agent remain in the cured product, and the volatilization of these residues may contribute to gas release. However, if the resin has a group represented by formula (3-1), the residue is the ring-closed resin. Therefore, it is believed that the problem of low-molecular-weight compounds remaining in the film after the heating step is resolved, and the amount of gas release is reduced.

[0105] When the specific resin has a group represented by formula (3-1), it is preferable that the specific resin produces an alkali at any temperature between 120 and 180°C. Furthermore, it is preferable that the specific resin produces an alkali during the heating process described above. Whether the specific resin produces an alkali at a certain temperature X°C can be determined by the following method: After heating 1 mole of the specific resin in a sealed container at 1 atmosphere pressure for 3 hours at the aforementioned X°C, the amount of decomposition can be quantitatively determined by methods such as HPLC (High Performance Liquid Chromatography) to determine whether an alkali is produced. It is preferable that the amount of alkali produced is 0.1 moles or more, and more preferably 0.5 moles or more. There is no particular upper limit to the amount of alkali produced; for example, it can be set to 1000 moles or less.

[0106] It is preferable that the molecular weight of the base produced from the specific resin is 40 to 1,000, more preferably 40 to 500, and even more preferably 50 to 400. It is preferable that the boiling point of the above-mentioned base having a pyridine structure at 1 atmosphere is 50 to 600°C, more preferably 50 to 500°C, and even more preferably 50 to 450°C.

[0107] It is preferable for the base produced to be a conjugate acid with a pKa of 0 or higher, more preferably 3 or higher, and even more preferably 6 or higher. There is no specific upper limit to the pKa of the aforementioned conjugate acid, but 30 or lower is preferred. pKa is the equilibrium constant Ka, which is expressed as the negative logarithm of the dissociation reaction of the acid releasing hydrogen ions. In this specification, unless otherwise specified, pKa is set as a value calculated based on ACD / ChemSketch (registered trademark). When there are multiple pKas of the aforementioned conjugate acid, at least one is preferably within the above range.

[0108] In formula (3-1), Z1 and Z2 independently represent organic groups. Preferably, the hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O)2-, and -NRN- is preferred. Preferably, the hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O- is also preferred. RN is as described above. The hydrocarbon group can be any one of an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred, and a saturated aliphatic hydrocarbon group being more preferred. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 8. Furthermore, the aliphatic hydrocarbon group can be any one of a straight-chain, branched, or cyclic structure, or a structure represented by a combination of these. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10, and even more preferably 6. The aforementioned hydrocarbon group may have known substituents within the scope of achieving the effects of the present invention.

[0109] Furthermore, at least one of Z1 and Z2 having a polymerizable group is also one of the preferred embodiments of the present invention. Examples of polymerizable groups include free radical polymerizable groups, epoxy groups, oxybutyl groups, hydroxymethyl groups, alkoxymethyl groups, etc., with free radical polymerizable groups being preferred. As free radical polymerizable groups, groups having an vinyl unsaturated group are preferred, such as (meth)acryloxy, (meth)acrylamine, vinylphenyl, maleic anhydride, styrene, vinyl, (meth)allyl, etc. Among these, (meth)acryloxy is preferred from a reactivity point of view. These polymerizable groups can be directly bonded to the nitrogen atom in formula (3-1), or they can be bonded via a linker group such as a hydrocarbon group (e.g., an alkyl group).

[0110] Furthermore, in formula (3-1), Z1 and Z2 can be bonded to form a ring structure. The formed ring structure can be an aromatic ring structure or an aliphatic ring structure, with an aliphatic ring structure being preferred, and a saturated aliphatic ring structure being even more preferred. As the above-mentioned ring structure, a cyclic amine having 2 to 10 carbon atoms is preferred; examples include pyrrolidine rings, piperidine rings, α-linoline rings, octahydroindole rings, octahydroisoindole rings, pyrrole rings, and pyridine rings, with pyrrolidine rings, piperidine rings, or α-linoline rings being preferred. Furthermore, the above-mentioned ring structure can have substituents within the range of achieving the effects of the present invention. Examples of substituents include hydrocarbon groups and halogen atoms. Examples of ring structures substituted by substituents include dimethylpiperidine rings.

[0111] It is preferred that the group represented by formula (3-1) is represented by formula (3-1-1) or formula (3-1-2). [Chemical Formula 17] In formula (3-1-1), Cy represents an aliphatic ring structure or an aromatic ring structure, and * indicates a bond site with other structures. In formula (3-1-2), Z3 and Z4 independently represent alkyl groups, and * indicates a bond site with other structures.

[0112] In formula (3-1-1), the ring structure represented by Cy is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure. Examples of ring structures represented by Cy include pyrrolidine rings, piperidine rings, α-linolenic rings, octahydroindole rings, octahydroisoindole rings, pyrrole rings, and pyridine rings, with pyrrolidine rings, piperidine rings, or α-linolenic rings being preferred. Furthermore, the ring structure represented by Cy may contain substituents within the range of effects obtained in this invention. Examples of substituents include hydrocarbon groups and halogen atoms. Examples of ring structures substituted by substituents include dimethylpiperidine rings.

[0113] In formula (3-1-2), Z3 and Z4 independently represent alkyl groups, with alkyl groups having 1 to 20 carbon atoms being preferred, alkyl groups having 1 to 10 carbon atoms being more preferred, and alkyl groups having 1 to 8 carbon atoms being even more preferred. The aforementioned alkyl groups can be any of the following structures: straight-chain, branched, or cyclic, or can be a structure represented by a combination of these.

[0114] The following are specific examples of groups represented by formula (3-1), but are not limited to them. [Chemical Formula 18]

[0115] The proportion of the total molar amount of the groups represented by formula (3-1) in a particular resin relative to the total molar amount of -A2-R113 and -A1-R114 in formula (2) and -A2-R113 in formula (PAI-2) described later is preferably 0.1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. The total molar amount of -A2-R113 and -A1-R114 in formula (2) and -A2-R113 in formula (PAI-2) described later, and the total molar amount of the groups represented by formula (3-1), can be calculated, for example, by NMR (nuclear magnetic resonance imaging). Furthermore, considering the reasons of improving drug resistance and pattern formation, the proportion of the total mole amount of the group represented by formula (3-1) relative to the total mole amount of -A2-R113 and -A1-R114 in formula (2) and -A2-R113 in formula (PAI-2) is preferably 99.9 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and especially preferably 80 mol% or less. Furthermore, considering the rationale of promoting the cyclization of polyimide precursor resin and polyamide-imide precursor resin to lower the heating temperature in the heating step and increase the elongation at break, it is preferable that the proportion of the molar amount of the group represented by formula (3-1) relative to the total molar amount of -A2-R113 and -A1-R114 in formula (2) and -A2-R113 in formula (PAI-2) described later in a specific resin is 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and especially preferably 98 mol% or more. A preferred embodiment of the invention is a state in which the proportion of the molar amount of the group represented by formula (3-1) relative to the total molar amount of -A2-R113 and -A1-R114 in formula (2) and -A2-R113 in formula (PAI-2) described later in formula (3-1) is 100 mol%.

[0116] Furthermore, the molar content of the group represented by formula (3-1) contained in the specific resin relative to the total mass of the specific resin is preferably 0.001 to 10 mmol / g, more preferably 0.01 to 5 mmol / g, and even more preferably 0.1 to 3 mmol / g. Also, the mass content of the group represented by formula (3-1) contained in the specific resin relative to the total mass of the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%, and even more preferably 1 to 20%.

[0117] Furthermore, it is also preferable that the polyimide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0118] Furthermore, in order 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.

[0119] 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 a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased. Formula (2-A) [Chemical Formula 19] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 each independently represent divalent organic groups, R113 and R114 each independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group, preferably both of which are groups containing polymerizable groups.

[0120] 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. R112 has the same meaning as R112 in equation (5), and the preferred range is also the same.

[0121] The polyimide precursor may contain one repeating unit represented by formula (2), or it may contain two or more repeating units. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0122] As one embodiment of the polyimide precursor of the present invention, an example is provided in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, further preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal units can be repeating units represented by formula (2).

[0123] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is even more preferred. In this specification, the molecular weight dispersion is a value calculated by dividing the weight-average molecular weight by the 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 above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated when the multiple polyimide precursors are considered as a single resin are each within the above-mentioned ranges.

[0124] 〔Polybenzoxazole precursor〕 The structure of the polybenzoxazole precursor used in this invention is not particularly limited, but it is preferred to contain repeating units represented by the following formula (3). [Chemical Formula 20] In formula (3), R121 represents a divalent organic group, R122 represents a tetravalent organic group, and R123 and R124 each independently represent a hydrogen atom or a monovalent organic group.

[0125] In formula (3), R123 and R124 have the same meaning as R113 in formula (2), and the preferred range is also the same. That is, it is preferred that at least one is a polymerizable group. In formula (3), R121 represents a divalent organic group. As a divalent organic group, it is preferred that the group includes at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. It is preferred that R121 is a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

[0126] As a dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, with dicarboxylic acid residues containing an aromatic group being more preferred. As a dicarboxylic acid containing an aliphatic group, dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkyl group. Examples of dicarboxylic acids containing straight-chain aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylhimelic acid. Diacid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid Acid, behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula, etc.

[0127] [Chemical Formula 21] (where Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0128] As a dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH groups is even more preferred.

[0129] [Chemical Formula 22] In the formula, A represents a divalent group selected from the group including -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0130] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

[0131] In formula (3), R122 represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R115 in formula (2) above, and the preferred range is also the same. Furthermore, it is preferable that R122 is 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 sulfonate, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfonate, 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.

[0132] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic groups are preferred.

[0133] [Chemical Formula 23] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -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. When R122 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 R122 in formula (3) and the other two are bonded to the oxygen atom of R122 in formula (3). It is even better that two asterisks are bonded to the oxygen atom of R122 in formula (3) and two # are bonded to the nitrogen atom of R122 in formula (3) or two asterisks are bonded to the nitrogen atom of R122 in formula (3) and two # are bonded to the oxygen atom of R122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom of R122 in formula (3) and two # are bonded to the nitrogen atom of R122 in formula (3).

[0134] Diaminophenol derivatives represented by formula (As) are also preferred. [Chemical Formula 24]

[0135] In formula (As), R1 is an organic group selected from the group consisting of hydrogen atom, alkyl group, substituted alkyl group, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or 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.

[0136] [Chemical Formula 25] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0137] It is believed that in the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, will make the carbonyl carbon of the amide bond closer to the hydroxyl group, and is particularly good from the perspective of further improving the effect of increasing the cyclization rate during hardening at low temperature.

[0138] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, which can maintain the effect of high transparency to i-rays and high cyclization rate when hardening at low temperature.

[0139] Furthermore, in the above formula (As), it is even more preferable that R1 is an alkylene group or a substituted alkylene group. Specific examples of alkylene groups and substituted alkylene groups related to R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable, considering the effects of maintaining high transparency to i-rays and high cyclization rate during low-temperature curing while also having sufficient solubility in solvents and being able to obtain a well-balanced polybenzoxazole precursor.

[0140] As a method for manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

[0141] As a specific example of the structure of a diaminophenol derivative represented by the above formula (As), the contents described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506 are provided, and such contents are incorporated herein by reference. Of course, it is not limited to such contents.

[0142] In addition to the repeating unit of formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units. From the viewpoint of being able to suppress the warping that accompanies the ring closure, it is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0143] [Chemical Formula 26] In formula (SL), Z has an a structure and a b structure, R1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R2s is a hydrocarbon group having 1 to 10 carbon atoms, at least one of R3s, R4s, R5s, and R6s is an aromatic group, and the remaining part is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may 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.

[0144] In formula (SL), Z is preferably a structure where R5s and R6s are phenyl. Furthermore, the molecular weight of the structure represented by 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 polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, while simultaneously achieving the effects of suppressing warpage and improving solvent solubility.

[0145] When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as a repeating unit. As an example of such a tetracarboxylic acid residue, R115 in formula (2) can be cited.

[0146] For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Also, 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 dispersion of the molecular weight of the above-mentioned polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no particular upper limit to the dispersion of the molecular weight of the polybenzoxazole precursor; for example, 2.6 or lower is preferred, 2.5 or lower is more preferred, 2.4 or lower is even more 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 dispersity of at least one polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated when the multiple polybenzoxazole precursors are considered as a single resin are each within the above-mentioned ranges.

[0147] 〔Polyamide-imide precursor〕 It is preferable that the polyamide-imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical Formula 27] In formula (PAI-2), R117 represents a trivalent organic group, R111 represents a divalent organic group, A2 represents an oxygen atom or -NRz-, R113 represents a hydrogen atom or a monovalent organic group, and Rz represents a hydrogen atom or a monovalent organic group.

[0148] In formula (PAI-2), R117 may be an example of a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these groups by a single bond or a linking group. It is preferred that 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 a group formed by combining two or more of these groups by a single bond or a linking group. It is even more preferred that an aromatic group with 6 to 20 carbons, or a group formed by combining two or more aromatic groups with 6 to 20 carbons by a single bond or a linking group, is formed. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is preferred; -O-, -S-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is even more preferred. As the alkylene group mentioned above, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is even more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the alkyl halogenate mentioned above, an alkyl halogenate having 1 to 20 carbon atoms is preferred, an alkyl halogenate having 1 to 10 carbon atoms is even more preferred, and an alkyl halogenate having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the alkyl halogenate 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 replaced by halogen atoms, but replacement of all hydrogen atoms by halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, phenyl groups are more preferred, and 1,3-phenyl or 1,4-phenyl groups are even more preferred.

[0149] Furthermore, from the viewpoint of suppressing the release of gas from the hardened material, it is preferable that R117 is a group represented by any one of the following formulas (X2-1) to (X2-3) or a group containing one or more aliphatic ring structures. [Chemical Formula 28] In formula (X2-1), R represents a substituent, n2 represents an integer from 0 to 2, and * represents the bonding site with other structures. In formula (X2-2), R independently represents a substituent, m2 represents an integer from 0 to 3, m3 represents an integer from 0 to 4, and * represents the bonding site with other structures. In formula (X2-3), R independently represents a substituent, m2 represents an integer from 0 to 2, m3 represents an integer from 0 to 3, L2 represents -CRC2-, -S(=O)2- or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures.

[0150] In formula (X2-1), the preferred state of R is the same as the preferred state of R in formula (W1-1) above. In formula (X2-1), n2 being 0 or 1 is preferred. In formula (X2-2), the preferred state of R is the same as the preferred state of R in formula (W1-1) above. In formula (X2-2), m2 being 0 or 1 is preferred. In formula (X2-2), m3 being 0 or 1 is preferred. In formula (X2-3), the preferred state of R is the same as the preferred state of R in formula (W1-1). In formula (X2-3), m2 being 0 or 1 is preferred. In formula (X2-3), m3 being 0 or 1 is preferred. In equation (X2-3), L2 represents -CRC2-, -S(=O)2-, or -O-, with -S(=O)2- being preferred. In equation (X2-3), the preferred state of RC is the same as the preferred state of R in equation (W1-1).

[0151] Specific examples of groups formed by any one of the groups represented in formulas (X2-1) to (X2-3) or groups containing one or more aliphatic ring structures can be given as follows, but are not limited thereto. In the following structures, * indicates a bond site with other structures. [Chemical Formula 29]

[0152] Furthermore, when a particular resin contains a group represented by any one of formulas (X2-1) to (X2-3), it is preferable that the particular resin contains, for example, the following structure: [Chemical Formula 30]

[0153] The preferred state of the aliphatic ring structure in the group comprising one or more aliphatic ring structures is the same as the preferred state of the aliphatic ring structure in the group comprising one or more aliphatic ring structures in R111 above.

[0154] Furthermore, R117 is preferably derived from a tricarboxylic acid compound with at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the aforementioned tricarboxylic acid compound can be anhydride-substituted. Examples of halogenable tricarboxylic acid compounds for manufacturing polyamide imine precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. Only one type of such tricarboxylic acid compound may be used, or two or more types may be used.

[0155] 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 group formed by combining two or more of these groups by a single bond or a linking group, is preferred. A tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group, is even more preferred.

[0156] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride), and benzoic acid linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or an extended phenyl group. These compounds can be compounds formed by anhydridating two carboxyl groups (e.g., trimellitic anhydride) or compounds formed by halogenating at least one carboxyl group (e.g., trimellitic anhydride chloride).

[0157] In formula (PAI-2), R111, A2, R113, and RZ have the same meaning as R111, A2, R113, and RZ in formula (2) above, and the better state is also the same.

[0158] The polyamide imide precursor may further include other repeating units. Examples of other repeating units include repeating units represented by formula (2) above, repeating units represented by formula (PAI-1) below, etc. [Chemical Formula 31]

[0159] In formula (PAI-1), R116 represents a divalent organic group, and R111 represents a divalent organic group. In formula (PAI-1), R116 may represent a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these groups by single bonds or linking groups. It is preferred that a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. It is even more preferred that an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups with 6 to 20 carbon atoms by single bonds or linking groups, is formed. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is preferred; -O-, -S-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is even more preferred. As the alkylene group mentioned above, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is even more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the alkyl halogenate mentioned above, an alkyl halogenate having 1 to 20 carbon atoms is preferred, an alkyl halogenate having 1 to 10 carbon atoms is even more preferred, and an alkyl halogenate having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the alkyl halogenate 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 replaced by halogen atoms, but replacement of all hydrogen atoms by halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, phenyl groups are more preferred, and 1,3-phenyl or 1,4-phenyl groups are even more preferred.

[0160] Furthermore, R116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. 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 compound. The carboxyl groups in the dicarboxylic acid dihalide compound can be halogenated, for example, chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides that can be used as precursors for manufacturing polyamide imide include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. Only one of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more may be used.

[0161] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide compound 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 group formed by combining two or more of these groups by a single bond or a linking group. It is even more preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide compound contains an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.

[0162] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, and azelaic acid. Examples of dicarboxylic acid dihalides include sebacic acid, hexafluorosebacic acid, 1,9-azelic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanic acid, octadecanoic acid, nonadecananoic acid, eicosanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanic acid, octadecanoic acid, nonadecananoic acid, triadecanoic acid, triadecanoic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of dicarboxylic acid dihalides include compounds with structures where two carboxyl groups are halogenated.

[0163] In formula (PAI-1), R111 has the same meaning as R111 in formula (2) above, and the better state is also the same.

[0164] Furthermore, it is preferable that the polyamide imide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyamide imide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0165] 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.

[0166] As one embodiment of the polyamide imide precursor of the present invention, an embodiment in which the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, more preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide imide precursor except for the terminal can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, further preferable that it is 90 mol% or more, and particularly preferable that it exceeds 90 mol%. The upper limit of the total content is not particularly limited; all repeating units in the polyamide-imide precursor, except for the terminal units, can be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0167] The weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferably, and 6.0 or lower is even more preferably. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when considering the multiple polyamide-imide precursors as a single resin are each within the aforementioned ranges.

[0168] [Manufacturing Method of Polyimide Precursors, etc.] For example, polyimide precursors, etc., can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature; a method of obtaining polyamide by reacting tetracarboxylic dianhydride with diamine at low temperature and then esterifying it with a condensing agent or an alkylating agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Of the above manufacturing methods, the method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting it with diamine is more preferred. Examples of condensing agents include dicyclohexanediimide, 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 include thionyl chloride, oxalyl chloride, and phosphatidyl chloride. In the method for manufacturing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the manufacturing method of 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 determined according to the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacrylbicyclo[5.4.0]undecyl-7-ene, N,N-dimethyl-4-aminepyridine, etc.

[0169] -End-capping agent- In the manufacture of polyimide precursors, etc., it is preferable to block the carboxylic anhydride, anhydride derivatives, or amine groups remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When blocking the carboxylic anhydride and anhydride derivatives remaining at the resin ends, monools, phenols, thiols, benzenethiophenols, monoamines, etc. can be used as end-capping agents. Considering reactivity and film stability, monools, phenols, and monoamines are preferred. Preferred compounds as monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butanol, adamantanol and other tertiary alcohols. Preferred compounds among phenols include phenol, methoxyphenol, methylphenol, naphth-1-ol, naphth-2-ol, 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, 1-carboxy-5-aminonaphthalene, and 2-carboxy-7-aminonaphthalene. -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 multiple different end groups can be introduced by reacting multiple end-capping agents. Furthermore, when blocking the amino groups at the resin ends, compounds with functional groups that can react with amino groups can be used for blocking. Preferred end-capping agents for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphen-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetic acid chloride, acrylonitrile chloride, propionic acid chloride, methacrylic acid chloride, neopentyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamon chloride, 1-adamantanemethyl chloride, heptafluorobutyl chloride, stearyl chloride, and benzoyl chloride.

[0170] Furthermore, as a capping agent, a compound represented by formula (T-1) can be used. It is believed that by using such a compound to seal the end, a structure that easily generates alkali can be introduced at the end, and even when hardened at low temperature, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin can be easily increased. [Chemical Formula 32] In formula (T-1), LT represents a divalent organic group, Z1 and Z2 represent organic groups independently, and Z1 and Z2 can be bonded to form a ring structure.

[0171] In formula (T-1), LT is preferably a hydrocarbon group, which can be any one of an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably any one of an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group. The linking chain length in LT (i.e., the smallest number of atoms among the two carbonyl groups bonded to LT) is preferably 2 to 4, with 2 being more preferred. In formula (T-1), Z1 and Z2 have the same meaning as Z1 and Z2 in formula (3-1), and the preferred states are also the same. In particular, at least one of Z1 and Z2 having a polymerizable group is also one of the preferred states of the present invention. Examples of polymerizable groups include free radical polymerizable groups, epoxy groups, oxybutyl groups, hydroxymethyl groups, alkoxymethyl groups, etc., with free radical polymerizable groups being preferred. As a free radical polymerizable group, a group having an vinyl unsaturated group is preferred, and examples include (meth)acryloxy, (meth)acrylamine, vinylphenyl, maleic anhydride, styryl, vinyl, and (meth)allyl. Among these, (meth)acryloxy is preferred from a reactivity point of view. These polymerizable groups can be directly bonded to the nitrogen atom in formula (T-1) or can be bonded via a linker group such as a hydrocarbon group (e.g., an alkyl group).

[0172] Specific examples of compounds represented by formula (T-1) include the following compounds, but are not limited thereto. [Chemical Formula 33]

[0173] - Solid Precipitation - When manufacturing polyimide precursors, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor, etc. To improve the purification degree, the polyimide precursor, etc., may be repeatedly subjected to operations such as redissolving, redepositing, and drying. A step of removing ionic impurities using an ion exchange resin may also be included.

[0174] [Content] Furthermore, the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more, relative to the total solid content of the resin composition. Here, from the viewpoint of suppressing the amount of gas release generated, the state in which the resin composition of the present invention contains a solvent and the content of the precursor of the above-mentioned cyclized resin is 70% by mass or more, relative to the total solid content of the resin composition, is also one of the preferred states of the present invention. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or it may contain two or more. When containing two or more, it is preferable that the total amount is within the above-mentioned range.

[0175] Furthermore, it is preferable that the resin composition of the present invention contains at least two types of resins. Specifically, the resin composition of the present invention may contain two or more types of specific resins and other resins described below, or it may contain two or more types of specific resins, and it is preferable that it contains two or more types of specific resins. When the resin composition of the present invention contains two or more types of specific resins, it is preferable that it contains, for example, two or more polyimide precursors with different structures derived from dianhydrides (R115 in formula (2) above).

[0176] <Other Resins> The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained. For example, by adding (meth)acrylic resin to the resin composition to replace the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the content of polymerizable groups in 1g of resin is 1×10-3 moles / g or more).

[0177] When the resin composition of the present invention includes other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the content of other resins in the resin composition of the present invention relative to the total solid content of the resin composition is preferably 80% by mass or less, 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. Also, 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-described samples, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, 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; 0% by mass or more is acceptable. The resin composition of the present invention may contain only one type of other resin, or it may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above-described range.

[0178] <Polymerizable Compound> It is preferable that the resin composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0179] It is preferable that the resin composition of the present invention contains a polymeric compound with a boiling point of 200°C or higher at 1 atmosphere. A boiling point of 200°C or higher is preferred, and 250°C or higher is even more preferred. Furthermore, the upper limit of the boiling point is not particularly limited; for example, 500°C or lower is acceptable. According to the above description, the amount of gas released can be reduced.

[0180] The polymeric compound with a boiling point of 200°C or higher at 1 atmosphere is preferably a compound having 3 or more polymeric groups, more preferably a compound having 4 or more polymeric groups, and even more preferably a compound having 5 or more polymeric groups. There is no particular limit to the number of polymeric groups, but 20 or less is preferred. Furthermore, the polymeric compound with a boiling point of 200°C or higher at 1 atmosphere is preferably a compound having 3 or more (meth)acrylate groups, more preferably a compound having 4 or more (meth)acrylate groups, and even more preferably a compound having 5 or more (meth)acrylate groups. There is no particular limit to the number of (meth)acrylate groups, but 20 or less is preferred.

[0181] Specific examples of polymeric compounds with a boiling point of 200°C or higher at 1 atmosphere include dinepentylenetetroxide hexaacrylate, neopentylenetetroxide tetraacrylate, neopentylenetetroxide tetramethacrylate, ditrimethylolpropane tetraacrylate, and ethoxylated dinepentylenetetroxide polymethacrylate. Furthermore, these compounds, whether acrylates or methacrylates, can be used as long as their boiling point is 200°C or higher. Commercially available products can be used as these compounds; for example, compounds manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

[0182] Furthermore, from the viewpoint of suppressing the amount of gas released from the hardened material, it is preferable that the resin composition contains a polymeric compound having an aliphatic ring structure. The polymeric compound may have only one polymeric group, but having two or more is preferable, having 2 to 10 is more preferable, having 2 to 6 is further preferable, and having 4 to 6 is particularly preferable. The aliphatic ring structure can be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure. Furthermore, the aliphatic ring structure can be a monocyclic ring, or a condensation ring, a cross-linked condensation ring, a spirocyclic ring, or other heterocyclic rings. Examples of the aliphatic ring structure include cyclohexane, cyclohexene, and bicyclic [2.2.2]octyl-5-ene structures.

[0183] [Free Radical Crosslinking Agent] It is preferable that the resin composition of the present invention includes a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As a free radical polymerizable group, it is preferable that it includes a group having an ethylene unsaturated bond. Examples of groups having an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acrylyl, maleicadiimino, (meth)acrylamide, etc. Among these, (meth)acrylyl, (meth)acrylamide, and vinylphenyl are preferred as groups having an ethylene unsaturated bond, and (meth)acrylyl is more preferred from the viewpoint of reactivity.

[0184] It is preferable that the free radical crosslinking agent is a compound having one or more ethylene unsaturated bonds, and even more preferably a compound having two or more ethylene unsaturated bonds. The free radical crosslinking agent may have three or more ethylene unsaturated bonds. As a compound having two or more of the above-mentioned ethylene unsaturated bonds, a compound having 2 to 15 ethylene unsaturated bonds is preferable, a compound having 2 to 10 ethylene unsaturated bonds is more preferable, and a compound having 2 to 6 ethylene unsaturated bonds is even more preferable. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured material), it is also preferable that the resin composition of the present invention includes compounds having two ethylene unsaturated bonds and compounds having three or more of the above-mentioned ethylene unsaturated bonds.

[0185] It is preferable that the molecular weight of the free radical crosslinking agent is 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. It is preferable that the lower limit of the molecular weight of the free radical crosslinking agent is 100 or more.

[0186] Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. 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 are preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Additionally, as another example, compounds substituted with unsaturated phosphonic acids, styrene, vinylbenzene derivatives, vinyl ethers, or allyl ethers can be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0187] Furthermore, it is preferable that the free radical crosslinking agent is a compound having a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetramethylolethane tri(meth)acrylate, neopentyl tetramethylolethane tetra(meth)acrylate, dinepentyl tetramethylolethane penta(meth)acrylate, dinepentyl tetramethylolethane hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol, or trimethylolethane, which are added to a polyfunctional alcohol and then subjected to (meth)acrylate reaction with ethylene oxide or propylene oxide. Esterified compounds, urethane (meth)acrylates described in Japanese Patent Application Publications Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Application Publications Nos. 48-064183, 49-043191, and 52-030490, multifunctional acrylates or methacrylates such as epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds such as glycidyl (meth)acrylate that have cyclic ether groups and vinyl unsaturated bonds.

[0188] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a cycloid and having two or more groups having ethylene unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0189] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, etc., can also be used. Furthermore, 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.

[0190] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 are also preferably used, and such contents are incorporated in this specification.

[0191] Furthermore, the compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) together with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then esterifying it with (meth)acrylate.

[0192] 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 in this specification.

[0193] As a free radical crosslinking agent, 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., 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., 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. Oligopolymer types such as these can also be used.

[0194] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methacrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentyloyl groups manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyloyl groups manufactured by Nippon Kayaku Co., Ltd.; UAS-10 and UAB-140, carbamate oligomers manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.; NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). Products manufactured by Kayaku Co., Ltd. include UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and BLEMMER PME400 (manufactured by NOF CORPORATION.).

[0195] As free radical crosslinking agents, urethane 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 urethane ester compounds having 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 with an amino group structure or a thioether structure 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.

[0196] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical crosslinking agent having acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and even more preferable is a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is neopentyl tetrol or dinepentyl tetrol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0197] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0198] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diacrylate. Dimethacrylates, dimethyloltricyclodecane diacrylates, dimethyloltricyclodecane dimethacrylates, ethylene oxide (EO) adduct diacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct diacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified diacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates having urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylates with a molecular weight of approximately 200. From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured material), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As monofunctional free radical crosslinking agents, the following are preferred: n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl (meth)acrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactone, and allyl glycidyl ether. For monofunctional free radical crosslinking agents, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred to suppress pre-exposure volatilization. Furthermore, as multifunctional or higher free radical crosslinking agents, allyl compounds such as diallyl phthalate and triallyl trimellitate are also suitable.

[0199] When a free radical crosslinking agent is contained, it is preferable that its content relative to the total solids content of the resin composition in this 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.

[0200] A single free radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used simultaneously, it is preferable that their total dosage be within the range mentioned above.

[0201] [Other Crosslinking Agents] It is preferable that the resin composition of the present invention includes other crosslinking agents different from the free radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. It is preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by the photosensitivity of the photoacid generator or photobase generator described above. It is even preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by the action of an acid or base. It is preferable that the acid or base described above is an acid or base generated from the photoacid generator or photobase generator during the exposure step. As other crosslinking agents, it is preferable that the compound has at least one group selected from the group including acetoxymethyl, hydroxymethyl and alkoxymethyl, and it is even preferable that the compound has a structure in which at least one group selected from the group including acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having the following structure: a structure in which an amine-containing compound such as melamine, acetylenurea, urea, alkylurea, or benzoguanidine is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atoms of the aforementioned amine groups are replaced with acetoxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, it can be an oligomer formed by the self-condensation of the hydroxymethyl groups of these compounds. As the aforementioned amine-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenurea, urea, or alkylurea are called urea-based crosslinking agents, crosslinking agents using alkylurea are called alkylurea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents. In these embodiments, it is preferable that the resin composition of the present invention comprises 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 comprises at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0202] As a compound containing at least one of alkoxymethyl and acetoxymethyl groups in this invention, examples of compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted on the nitrogen atom or trimethylol group of the aromatic group or the urea structure described below are provided as structural examples. Regarding the alkoxymethyl or acetoxymethyl group in the above-mentioned compound, it is preferred that the number of carbon atoms is 2 to 5, more preferably 2 or 3, and even more preferably 2. It is preferred that the total number of alkoxymethyl and acetoxymethyl groups in the above-mentioned compound is 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. It is preferred that the molecular weight of the above-mentioned compound is 1500 or less, and preferably 180 to 1200.

[0203] [Chemical Formula 34]

[0204] R100 represents an alkyl or acetyl group. R101 and R102 each independently represent a monovalent organic group that can bond with each other to form a ring.

[0205] Compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group can be exemplified by compounds of the following general formula.

[0206] [Chemical Formula 35]

[0207] In the formula, X represents a single bond or a divalent organic group, each R104 independently represents an alkyl or acetyl group, and R103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to generate a base-soluble group (e.g., a group that is released by the action of an acid, or a group represented by -C(R4)2COOR5 (R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group that is released by the action of an acid.)). Each R105 independently represents an alkyl or alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Regarding groups that decompose under the action of acid to generate base-soluble groups, groups that are released under the action of acid, and R5 in groups represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In these formulas, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can be bonded together to form a ring. Alkyl groups with 1 to 10 carbon atoms are preferred, and alkyl groups with 1 to 5 carbon atoms are more preferred. The alkyl groups can be either straight-chain or branched. Cycloalkyl groups with 3 to 12 carbon atoms are preferred, and cycloalkyl groups with 3 to 8 carbon atoms are more preferred. The cycloalkyl groups can be monocyclic or polycyclic structures such as condensed rings. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and phenyl is more preferred. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an alkyl group having 7 to 16 carbon atoms is more preferred. The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred states of these alkyl and aryl groups are the same as those of the alkyl and aryl groups mentioned above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is more preferred. Furthermore, these groups may further have known substituents within the scope of obtaining the effects of the present invention.

[0208] R01 and R02 independently represent hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkenyl.

[0209] Preferably, such groups are trialkyl esters, acetals, cumyl esters, enols, etc. More preferably, they are trialkyl esters or acetals.

[0210] Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acetoxymethyl group include compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group. Examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule include the following compounds, but are not limited to these.

[0211] [Chemical Formula 36]

[0212] [Chemical Formula 37]

[0213] Compounds containing at least one of alkoxymethyl and acetoxymethyl can be commercially available or synthesized by known methods. From the viewpoint of heat resistance, compounds in which the alkoxymethyl or acetoxymethyl is directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0214] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0215] Specific examples of urea-based crosslinking agents include, for example, monohydroxymethylated acetylenide, dihydroxymethylated acetylenide, trihydroxymethylated acetylenide, tetrahydroxymethylated acetylenide, monomethoxymethylated acetylenide, dimethoxymethylated acetylenide, trimethoxymethylated acetylenide, tetramethoxymethylated acetylenide, monoethoxymethylated acetylenide, diethoxymethylated acetylenide, triethoxymethylated acetylenide, tetraethoxymethylated acetylenide, monopropoxymethylated acetylenide, dipropoxymethylated acetylenide, tripropoxymethylated acetylenide, tetrapropoxymethylated acetylenide, monobutoxymethylated acetylenide, dibutoxymethylated acetylenide, tributoxymethylated acetylenide, or tetrabutoxymethylated acetylenide, etc.; urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, etc. Vinylurea crosslinking agents such as monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc.; propylene urea crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc.; 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

[0216] Specific examples of benzoguanidine crosslinking agents include, for example, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, etc.

[0217] In addition, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, 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) may also be used. Specific examples of such compounds include benzyl glycol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzene hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Ketones, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0218] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all 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, DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO.,LTD), etc.

[0219] 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]oxa compounds as other crosslinking agents.

[0220] -Epoxy compound (a compound having epoxy groups)- As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing the risk of film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition in this invention can be effectively suppressed.

[0221] It is preferable that the epoxy compound contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, preferably 2 to 15 repeating units.

[0222] Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and polysiloxanes containing epoxy groups such as polymethyl (epoxypropoxypropyl)siloxane, but are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by 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 trade 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 trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used preferentially.

[0223] [Chemical Formula 38]

[0224] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0225] In the above structure, considering both heat resistance and improved elongation, n is 1 to 2 and m is 3 to 7, which is better.

[0226] -Oxycyclobutane compounds (compounds having oxycyclobutane rings)- Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutane)methyl] ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. are preferred; these can be used alone or in mixtures of two or more.

[0227] -Benzoxazole compounds (compounds with benzoxazole groups)-Benzoxazole compounds are preferred because the cross-linking reaction caused by the ring-opening addition reaction does not produce gas release during hardening, thereby reducing thermal shrinkage and inhibiting warping.

[0228] Preferred examples of benzo[a]oxa compounds include Pd-type benzo[a]oxa, Fa-type benzo[a]oxa (trade names, manufactured by Shikoku Chemicals Corporation), benzo[a]oxa adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a]oxa compounds. These can be used alone or in combination of two or more.

[0229] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and especially preferably 1.0 to 10% by mass. Other crosslinking agents may be contained in only one type, or may contain two or more types. When two or more other thermal crosslinking agents are contained, it is preferable that their total content is within the above-mentioned range.

[0230] It is preferable that the resin composition of the present invention includes a photosensitizer. Examples of photosensitizers include photopolymerization initiators and photoacid generators, with photopolymerization initiators being preferred.

[0231] [Polymerization Initiator] It is preferable that the resin composition of the present invention contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferable to contain a photopolymerization initiator. It is preferable that the photopolymerization initiator is a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, it is preferable that the photoradical polymerization initiator is photosensitive to light in the ultraviolet to visible regions. In addition, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0232] 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 an ethyl acetate solvent at a concentration of 0.01 g / L with a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer).

[0233] 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 an oxadiazole 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 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0234] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0235] 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, as described in this specification.

[0236] As an α-hydroxy ketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF).

[0237] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0238] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which have absorption maximum wavelengths 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.

[0239] Examples of phosphine-based initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.

[0240] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0241] Oxime compounds are even better examples of photoradical polymerization initiators. By using oxime compounds, the exposure latitude can be further improved more effectively. Oxime compounds are particularly good because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0242] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2006-342166, the compounds described in Japanese Patent Application Publication No. 2017-019766, and the compounds described in Japanese Patent Publication No. 6065596. The compounds described herein include those described in 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.

[0243] Examples of preferred oxime compounds include compounds with the following structures: 3-benzyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonoxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have an intramolecular linker >C=NOC(=O)-.

[0244] [Chemical Formula 39]

[0245] 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 Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structure can also be used. [Chemical Formula 40]

[0246] 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, the contents of which are incorporated herein by reference.

[0247] As a photoradical polymerization initiator, oxime compounds having at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0248] 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 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, the contents of which are incorporated herein by reference.

[0249] Oxime compounds containing nitro groups can be used as photopolymerization initiators. It is also preferable that the oxime compound containing nitro groups is a dimer. Specific examples of oxime compounds containing nitro groups include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is also an example of an oxime compound containing nitro groups.

[0250] 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.

[0251] Oxime compounds with hydroxyl substituents bonded to the carbazole backbone can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0252] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group ArOX1 with an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic ArOX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred from the perspective of easily forming a film with excellent lightfastness, while benzoyl is further preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkyl hydrogen sulfide, aryl hydrogen sulfide, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkyl hydrogen sulfide, aryl hydrogen sulfide or amino are even more preferred, and alkoxy, alkyl hydrogen sulfide or amino are further preferred.

[0253] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 41] In this formula, RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphinyl, aminomethyl, or aminosulfonyl; RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; and RX3 to RX14 each independently represent a hydrogen atom or a substituent. At least one of RX10 to RX14 is an electron-withdrawing group.

[0254] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13 and RX14 are preferably hydrogen atoms.

[0255] As a specific example of an oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, the contents of which are incorporated herein by reference.

[0256] Examples of preferred oxime compounds include those with specific substituents disclosed in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups disclosed in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0257] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0258] It is even more preferable that the free radical polymerization initiator is a trihalomethane trihalomethane compound, an α-amino ketone 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, and is selected from at least one compound in the group including trihalomethane trihalomethane compound, α-amino ketone compound, metallocene compound, oxime compound, triarylimidazolium dimer, and benzophenone compound, and is even more preferable to use a metallocene compound or an oxime compound.

[0259] Furthermore, the photoradical polymerization initiator can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone) and other N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-hydroxyphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-hydroxyphenyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by cyclization with aromatic rings, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Also, compounds represented by the following formula (I) can be used.

[0260] [Chemical Formula 42]

[0261] In formula (I), RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, and 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 having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0262] [Chemical Formula 43]

[0263] In the formula, RI05~RI07 are the same as RI02~RI04 in the above formula (I).

[0264] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0265] As a photoradical polymerization initiator, a photoradical polymerization initiator with two or more functionalities can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thus obtaining good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases while the solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc., are included in this specification.

[0266] 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 range is preferred. Furthermore, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator; therefore, heating by an oven, heating plate, etc., may further promote crosslinking based on the photopolymerization initiator.

[0267] 〔Senser〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., and produces electron transfer, energy transfer, heating, etc. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazolomethoxymethyl, phthalocyanine, benzo[a]piperan, and indigo compounds 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-dimethylaminophenylallyl dihydroindone. Methylaminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-hydroxylinylbenzophenone, isoamyl dimethylaminobenzoate Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthyl(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Other sensitizing dyes may also be used. For detailed information on sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0268] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solid 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 alone, or two or more may be used simultaneously.

[0269] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, 3rd Edition (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds with thiocarbonyl sulfhydryl groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0270] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0271] 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 solid content 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.

[0272] <Alkali Generating Agent> The resin composition of the present invention may contain an alkali generating agent. Here, an alkali generating agent refers to a compound capable of generating an alkali through physical or chemical action. The alkali generating agent described herein does not include the specific resins mentioned above. As preferred alkali generating agents for the resin composition of the present invention, thermal alkali generating agents and photo-alkali generating agents are examples. 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 containing a thermal alkali generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product are improved, for example, the performance of the interlayer insulating film used in the redistribution layer of a semiconductor package is improved. As an alkali generating agent, it can be an ionic alkali generating agent or a nonionic alkali generating agent. As an alkali generated from the alkali generating agent, for example, secondary amines and tertiary amines are examples. The alkali generating agent of the present invention is not particularly limited, and known alkali generating agents can be used. Commonly known base-generating agents include, for example, aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide 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 aceoxyimine compounds. Specific compounds representing nonionic base-generating agents include those represented by formulas (B1), (B2), or (B3). [Chemical Formula 44]

[0273] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. Rb1 and Rb2 do not simultaneously become hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not have a carboxyl group. In addition, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to this when the bonded carbon atoms are carbon atoms forming a carbonyl group, that is, when they form an amide group together with the nitrogen atom.

[0274] 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 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.

[0275] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably with 2 to 18 carbon atoms, and further preferably with 3 to 12 carbon atoms), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably with 2 to 18 carbon atoms, and further preferably with 3 to 12 carbon atoms), aryl groups (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and further preferably with 6 to 10 carbon atoms), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably with 7 to 19 carbon atoms, and further preferably with 7 to 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. As the formed ring, a nitrogen-containing heterocycle with 4 to 7 members is preferred. In particular, Rb1 and Rb2 are preferably straight-chain, branched or cyclic alkyl groups with substituents (preferably 1 to 24 carbons, more preferably 2 to 18 carbons, and even more preferably 3 to 12 carbons), preferably cycloalkyl groups with substituents (preferably 3 to 24 carbons, more preferably 3 to 18 carbons, and even more preferably 3 to 12 carbons), and preferably cyclohexyl groups with substituents.

[0276] As Rb3, examples include alkyl groups (preferably with 1 to 24 carbons, more preferably with 2 to 18, and further preferably with 3 to 12), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18, and further preferably with 6 to 10), alkenyl groups (preferably with 2 to 24 carbons, more preferably with 2 to 12, and further preferably with 2 to 6), and aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19, and further preferably with 7 to 12). The preferred substituents are alkyl (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 are preferred. Rb3 may further have substituents within the scope of achieving the effects of this invention.

[0277] The compound represented by formula (B1) is preferably represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 45]

[0278] In the formula, Rb11 and Rb12, and Rb31 and Rb32 have the same meaning as Rb1 and Rb2 in formula (B1), respectively. Rb13 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and further preferably with 3 to 12 carbons), an alkenyl group (preferably with 2 to 24 carbons, more preferably with 2 to 18 carbons, and further preferably with 3 to 12 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and further preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and further preferably with 7 to 12 carbons), and may have substituents within the range of exerting the effects of the present invention. Among them, it is preferred that Rb13 is an aralkyl group.

[0279] Rb33 and Rb34 are each independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 8 carbon atoms, and even more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 8 carbon atoms, and even more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms), an aralkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and even more preferably with 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0280] Rb35 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), with an aryl group being preferred.

[0281] The compound represented by formula (B1-1) is preferred over the compound represented by formula (B1-1a). [Chemical Formula 46]

[0282] Rb11 and Rb12 have the same meaning as Rb11 and Rb12 in formula (B1-1). Rb15 and Rb16 are hydrogen atoms, alkyl (preferably 1-12 carbons, more preferably 1-6 carbons, and even more preferably 1-3 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-6 carbons, and even more preferably 2-3 carbons), aryl (preferably 6-22 carbons, more preferably 6-18 carbons, and even more preferably 6-10 carbons), aralkyl (preferably 7-23 carbons, more preferably 7-19 carbons, and even more preferably 7-11 carbons), hydrogen atoms, or methyl groups are preferred. Rb17 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), wherein an aryl group is preferred.

[0283] [Chemical Formula 47]

[0284] In formula (B3), L is a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the path of the linking chain. Also, RN1 and RN2 each independently represent a monovalent organic group.

[0285] In this specification, "linking chain" refers to an atomic chain that connects two atoms or groups of atoms along a path connecting the linked objects with the shortest (smallest number of atoms) distance. For example, in a compound represented by the following formula, L is composed of styrene, has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms along the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4. [Chemical Formula 48]

[0286] It is preferable that the number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is 3 to 24. An upper limit of 12 or less is more preferable, 10 or less is even more preferable, and 8 or less is particularly preferable. A lower limit of 4 or more is more preferable. From the viewpoint of facilitating the above-mentioned intramolecular cyclization reaction, an upper limit of 12 or less of the linking chain length of L is preferable, 8 or less is more preferable, 6 or less is even more preferable, and 5 or less is particularly preferable. In particular, a linking chain length of 4 or 5 is preferable, with 4 being optimal. Specific examples of preferred compounds as base-generating agents include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0287] Furthermore, it is preferable that the alkali-generating agent comprises a compound represented by the following formula (N1). [Chemical Formula 49]

[0288] 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.

[0289] L is a divalent linker, preferably a divalent organic group. 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 refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0290] In formula (N1), RN1 and RN2 are each independently a monovalent organic group (preferably with 1 to 24 carbons, more preferably 2 to 18, and further preferably 3 to 12), or a hydrocarbon group (preferably with 1 to 24 carbons, more preferably 1 to 12, and further preferably 1 to 10). Specifically, aliphatic hydrocarbon groups (preferably with 1 to 24 carbons, more preferably 1 to 12, and further preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbons, more preferably 6 to 18, and further preferably 6 to 10) are preferred. Aliphatic hydrocarbon groups are preferred. If aliphatic hydrocarbon groups are used as RN1 and RN2, the resulting base has higher basicity. Furthermore, aliphatic hydrocarbon groups and aromatic hydrocarbon groups can have substituents, and aliphatic hydrocarbon groups and aromatic hydrocarbon groups can also have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0291] Examples of aliphatic hydrocarbon groups constituting RN1 and RN2 include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups combining chain alkyl groups and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. It is preferred that the number of carbon atoms in the straight-chain or branched chain alkyl group is 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, etc. It is preferred that the number of carbon atoms in the cyclic alkyl group is 3 to 12, and more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. The carbon number of the group relating to the combination of chain alkyl and cyclic alkyl groups is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the groups relating to the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. The carbon number of the alkyl group containing an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group containing an oxygen atom 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 decomposition to form a base as described later, RN1 and RN2 are preferably alkyl groups with 5 to 12 carbons. In formulations where adhesion to metals (e.g., copper) is important, alkyl groups containing cyclic alkyl groups and having 1 to 8 carbons are preferred.

[0292] RN1 and RN2 can be linked together 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, with a monocyclic ring being preferred. As the formed ring structure, a 5-membered or 6-membered ring containing the 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 sulfoline rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperidine rings, and sulfoline rings are preferred.

[0293] RC1 represents a hydrogen atom or a protecting group, with hydrogen atom being preferred.

[0294] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid can be cited as an example.

[0295] 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, cyclohexyl, etc. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM), ethoxyethyl (EE), etc. Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, tetrahydropiperanyl (THP), etc.

[0296] There are no particular limitations on the divalent linker constituting 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 have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linker having an oxygen atom in the chain is preferred, and a group having an oxygen atom in the chain, 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 is even more preferred, and a divalent aliphatic hydrocarbon group having an oxygen atom in the chain is even more preferred. It is preferred that these groups do not have an oxygen atom. It is preferred that the number of carbon atoms in the divalent hydrocarbon linker is 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. It is preferred that the number of carbon atoms in the divalent aliphatic hydrocarbon group is 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (e.g., arylalkyl) is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0297] Specifically, as the linking group L, linear or branched chain-like alkylene groups, cyclic alkylene groups, groups relating to combinations of chain-like and cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear or branched chain-like alkenyl groups, cyclic alkenyl groups, aryl groups, and arylalkylene groups are preferred. The number of carbon atoms in the linear or branched chain-like alkylene groups is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms in the cyclic alkylene groups is preferably 3 to 12, and more preferably 3 to 6. The number of carbon atoms in the groups relating to combinations of chain-like and cyclic alkylene groups is preferably 4 to 24, more preferably 4 to 12, and further preferably 4 to 6. The alkylene groups having oxygen atoms in the chain can be chain-like or cyclic, and can be linear or branched. It is preferred that the number of carbon atoms in the alkyl group containing oxygen atoms in the chain is 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0298] The linear or branched chain alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenyl group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenyl group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylalkyl group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, aryl, and arylalkylene are preferred, and 1,2-vinyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and vinylethoxyethylene (especially 1,2-vinylethoxy-1,2-vinyl) are even more preferred.

[0299] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting.

[0300] [Chemical Formula 50]

[0301] It is preferable that the molecular weight of the nonionic alkali generator is below 800, more preferably below 600, and further preferably below 500. As a lower limit, it is preferable that the molecular weight is above 100, more preferably above 200, and further preferably above 300.

[0302] Specific examples of preferred compounds as ionic base generating agents include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0303] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 51]

[0304] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 52]

[0305] 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. The lower limit is preferably 0.3 parts by weight or more, and 0.5 parts by weight or more is further preferred. The upper limit is preferably 30 parts by weight or less, 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 two or more are used, the total amount is preferably within the above range. Furthermore, as described above, in the present invention, alkali can also be generated from a specific resin or contained in the developer or processing solution, or alkali or an alkali-generating agent can be allowed to permeate into the membrane. Therefore, it is possible to design a resin composition containing an alkali-generating agent and a cyclized resin or its precursor, with a reduced content of the alkali-generating agent compared to conventional resin compositions containing an alkali-generating agent and a cyclized resin or its precursor. As a result, it is believed that the residues of the alkali-generating agent after alkali generation, as well as the undecomposed alkali-generating agent itself, are less likely to remain in the composition, resulting in reduced gas release from the cured material and improved adhesion within the cured material. In this type of sample, it is preferable to set the alkali-generating agent content to 2% by mass or less relative to 100 parts by mass of the resin. Furthermore, it is preferable to set the alkali-generating agent content to 1% by mass or less relative to 100 parts by mass of the resin, and even more preferable to set it to 0.5% by mass or less. Furthermore, it is preferable to set the alkali-generating agent content to 0.1% by mass or less relative to 100 parts by mass of the resin. In these samples, the lower limit of the alkali-generating agent content can be 0% by mass. The alkali-generating agent content can be determined based on the type and amount of alkali generated from a specific resin, the type and amount of alkali contained in the developer or processing solution, heating conditions, etc.

[0306] <Solvent> It is preferable that the resin composition of the present invention contains a solvent. Any known solvent may be used. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, alcohols, and other compounds.

[0307] 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-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, alkyl 3-alkoxypropionate). Ethyl propionate, 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-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.

[0308] As ethers, examples of preferred choices 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 celusone acetate, ethyl celusone 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.

[0309] As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. are preferred.

[0310] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples.

[0311] As a sulfide, dimethyl sulfide is a preferred example.

[0312] Among 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-methoxycarbamate, and N-acetylcarbamate are preferred.

[0313] Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are preferred.

[0314] As alcohols, examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol, etc.

[0315] Regarding solvents, from the perspective of improving the properties of the coating surface, it is better to mix two or more forms.

[0316] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydro-L-glucanone, 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.

[0317] Regarding the solvent content, from the viewpoint of coatability, it is preferable that the total solids concentration of the resin composition in this invention is 5-80% by mass, more preferably 5-75% by mass, further preferably 10-70% by mass, and even more preferably 20-70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method.

[0318] The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferable that their total amount is within the above-mentioned range.

[0319] <Metal Adhesion Modifier> Preferably, the resin composition of the present invention includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having sulfonylurea structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0320] 〔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, the contents of which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Also, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0321] [Chemical Formula 53]

[0322] 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- Acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0323] 〔Aluminum-based adhesive aid〕 Examples of aluminum-based adhesive aids include tri(acetyl ethyl acetate) aluminum, tri(acetyl acetone) aluminum, and acetyl ethyl acetate diisopropyl aluminum.

[0324] 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 in this specification.

[0325] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes better; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become better. There may be only one type of metal adhesion modifier, or there may be two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[0326] <Migration Inhibitor> 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 inhibited.

[0327] As a migration inhibitor, there are no particular limitations, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, piperidine ring, 2H-piperanium ring and 6H-piperanium ring, triazine ring), compounds having 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.

[0328] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0329] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[0330] The following compounds can be cited as specific examples of migration inhibitors.

[0331] [Chemical Formula 54]

[0332] 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.

[0333] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

[0334] <Polymerization Inhibitor> It is preferable that the resin composition of the present invention includes 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.

[0335] Specific compounds used as polymerization inhibitors may preferably include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallnutol, p-tertiary butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxyamino cerium salt, N-nitroso-N-phenylhydroxyamino aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and 1-nitroso-2-naphthol. 2-Nitrosamino-1-naphthol, 2-Nitrosamino-5-(N-ethyl-N-sulfopropylamino)phenol, N-Nitrosamino-N-(1-naphthyl)hydroxyaminoammonium 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, phenanthrene, phenoxazone, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyl dithiocarbonate, nitrobenzene, aluminum N-nitroso-N-phenylhydroxylamine, ammonium N-nitroso-N-phenylhydroxylamine, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Patent Publication No. 2015 / 125469 can also be used; this information is incorporated herein by reference.

[0336] 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.

[0337] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0338] <Other Additives> The resin composition of the present invention can be combined with various additives as needed within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the 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, the contents of which are incorporated herein by reference. When these additives are used, it is preferable to set their total amount to less than 3% by mass of the solid component of the resin composition in this invention.

[0339] 〔Surfactant〕 As a surfactant, various surfactants such as fluorinated surfactants, polysiloxane surfactants, and hydrocarbon surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or anionic surfactant.

[0340] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to further and better form a film with a uniform thickness and less thickness unevenness.

[0341] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), and Surflon. S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorinated surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, the contents of which 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, the contents of which are incorporated herein by reference, can be cited. Fluorinated surfactants can also preferably be fluorinated polymers (including 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). The following compounds can also be cited as fluorinated surfactants used in this invention: [Chemical Formula 55]

[0342] The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Regarding fluorinated surfactants, fluoropolymers with vinyl unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0343] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness and liquid saving, and also have good solubility in the composition.

[0344] Examples of polysiloxane 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).

[0345] As hydrocarbon-based surfactants, examples 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, PIONIN P-4050-T, etc. (all manufactured by TAKEMOTO OIL & FAT CO.,LTD).

[0346] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO.,LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO.,Ltd.), etc.

[0347] Specifically, examples of cationic surfactants include organosiloxane polymers such as KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers such as POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0348] Specifically, examples of anionic surfactants include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0349] Only one type of surfactant may be used, or two or more types may be used in combination. The surfactant content relative to the total solid content of the composition is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass.

[0350] [Higher fatty acid derivatives] In order 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 are biased to the surface of the resin composition of the present invention during the drying process after coating.

[0351] Furthermore, higher fatty acid derivatives may also use compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0352] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[0353] [Thermal Polymerization Initiator] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy, initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiator also has the function of initiating polymerization by heat, and can sometimes be added as a thermal polymerization initiator.

[0354] As a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 are included in this specification.

[0355] 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.

[0356] [Inorganic Particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0357] 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 particularly preferably 0.04–0.5 μm. The aforementioned average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be determined by dynamic light scattering based on a Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.). If the above determination is difficult to perform, it can also be determined by centrifugal sedimentation transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0358] [Ultraviolet Absorber] The resin composition of the present invention may include an ultraviolet absorber. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triterpenoid-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-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, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. Butyl-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, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0359] Examples of acrylonitrile-based ultraviolet absorbers 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-dodecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[4-[(2-hydroxy-3-tridecoxypropyl)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-tris(hydroxyphenyl) compounds, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, etc.; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxyphenyl)phenyl]-1,3,5-tris(hydroxyphenyl) compounds, etc.

[0360] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more. The composition of this invention may or may not contain ultraviolet absorbers, but when ultraviolet absorbers are included, the content of ultraviolet absorbers relative to the total solid content of the composition of this invention is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[0361] [Organotitanium compound] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0362] As usable organotitanium compounds, those in which the organic group is bonded to the titanium atom via a covalent bond or an ionic bond can be cited. Specific examples of organotitanium compounds are shown in I) to VII) below. I) Chelated titanium compounds: Among them, chelated titanium compounds having two or more alkoxy groups are preferred from the perspective of excellent preservation stability of the resin composition and obtaining a good curing pattern. Specific examples are bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediol) titanium, diisopropoxybis(ethyl acetate) titanium, etc. II) Tetraalkoxy titanium compounds: Examples include tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Diocene titanium compounds: Examples include pentamethylcyclopentadienetrimethoxytitanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: Examples include tris(dioctyl phosphate)isopropoxytitanium, tris(dodecyl benzenesulfonate)isopropoxytitanium, etc. V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc. VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc. VII) Titanium ester coupling agents: such as isopropyltris(2-dimethylbenzenesulfonyl)titanate, etc.

[0363] Among these, from the viewpoint of exhibiting better drug resistance, it is preferable that at least one compound is selected from the group consisting of I) chelated titanium compounds, II) tetraalkoxy titanium compounds and III) diacetic titanium compounds. In particular, diisopropoxybis(acetyl ethyl acetate) titanium, tetra(n-butoxy) titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0364] When compounding with organotitanium compounds, the amount of compounding relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of compounding is 0.05 parts by weight or more, the obtained hardened pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0365] [Antioxidant] The resin composition of the present invention may include an antioxidant. By including an antioxidant as an additive, the tensile properties of the cured film and its adhesion to metal 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, regarding antioxidants, compounds having a phenolic group and a phosphite group in the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can also be preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-2-yl)oxy]ethyl]amine, and bis(2,4-di-tertiary butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Additionally, the resin composition of this invention may contain potential antioxidants as needed. As potential antioxidants, compounds in which the site of antioxidant activity is protected by a protecting group can be cited. In such compounds, the protecting group is removed by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst, thereby enabling the antioxidant to function. Compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants, the contents of which are incorporated herein by reference. Commercially available 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-bis-tert-butylphenol and compounds represented by formula (3).

[0366] [Chemical Formula 56]

[0367] 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 a 1 to 4 valent organic group comprising at least one of an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0368] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metal materials.

[0369] In order to act simultaneously on both the resin and the metal material, it is preferable that k is an integer from 2 to 4. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silicone, alkoxy silicone, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further have substituents. Among these, from the viewpoint of solubility in the developer and metal adhesion, alkyl ethers and -NH- are preferred, while from the viewpoint of interaction with the resin and metal adhesion based on the formation of metal complexes, -NH- is more preferred.

[0370] The following compounds are examples of compounds represented by general formula (3), but are not limited to the following structures.

[0371] [Chemical Formula 57]

[0372] [Chemical Formula 58]

[0373] [Chemical Formula 59]

[0374] [Chemical Formula 60]

[0375] 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 effects of tensile properties and improved adhesion to metal materials even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved by utilizing the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0376] [Anti-coagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0377] In this invention, one type of anti-coagulant may be used alone, or two or more may be used in combination. The resin composition of this invention may or may not contain an anti-coagulant, but when it does contain an anti-coagulant, the content of the anti-coagulant relative to the total solid content of the resin composition of this invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[0378] [Phenolic Compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

[0379] In this invention, one phenolic compound may be used alone, or two or more may be used in combination. The resin composition of this invention may or may not contain phenolic compounds, but when phenolic compounds are included, the content of phenolic compounds relative to the total solid content of the resin composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0380] 〔Other polymeric compounds〕 Examples of other polymeric compounds include silicone resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0381] In this invention, one or more other polymeric compounds may be used alone or in combination. The resin composition of this invention may or may not contain other polymeric compounds, but when they are included, the content of other polymeric compounds relative to the total solid content of the resin composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0382] <Characteristics of the Resin Composition> The viscosity of the resin composition in this invention can be adjusted according to the concentration of the solid components in the resin composition. From the viewpoint of coating film thickness, 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm² / s or more, it is easy to coat with the film thickness required as an insulating film for rewiring, and if it is 12,000 mm² / s or less, a coating film with excellent surface finish can be obtained.

[0383] <Limitations on the Contents of the Resin Composition> It is preferable that the moisture content of the resin composition in this invention is less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include humidity adjustment under storage conditions and reducing the porosity of the storage container during storage.

[0384] From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of such metals is within the above-mentioned range.

[0385] Furthermore, as a method for reducing metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0386] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, it is preferable that the halogen atom content is less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Among these, it is preferable that the content of halide ions is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chloride ions and bromide ions, is within the above-mentioned ranges. As a method for adjusting the halogen atom content, ion exchange treatment is a preferred example.

[0387] Furthermore, from the viewpoint of reducing the amount of gas released from the cured material, it is preferable that the content of the component with a molecular weight of 1000 or less and different from the solvent in the resin composition is 40% by mass or less relative to the total solid content of the resin composition. A molecular weight of 800 or less is preferable, and 600 or less is even more preferable. The lower limit of the molecular weight is not particularly limited; for example, it can be set to 50 or more. Furthermore, a content of 30% by mass or less is preferable, and 10% by mass or less is even more preferable. The lower limit of the content is not particularly limited; it can also be set to 0% by mass.

[0388] Conventionally known containers can be used as the container for the resin composition of the present invention. Furthermore, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with an inner wall composed of six types of six-layered resins, or bottles with a seven-layered structure formed by six types of resins, are also preferred as the container. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0389] (Resin Composition) The resin composition of the present invention is a resin composition containing a precursor of a cyclized resin, wherein, when measuring the glass transition temperature under the following measurement conditions 1, at least one of three films with different thicknesses has a glass transition temperature of 200°C or higher. Measurement Condition 1: The above-mentioned resin composition is coated on a silicon substrate with thicknesses of 5 μm, 10 μm, or 20 μm, respectively. After drying at 100°C for 5 minutes, a cured material is obtained by heating at 180°C for 2 hours. The glass transition temperature of the cured material cooled to 25°C is measured using a differential scanning calorimeter.

[0390] According to the resin composition of the present invention, a cured product with low gas release can be obtained. The mechanism for achieving the above-mentioned effect is not yet clear, but it is speculated to be as follows. When the glass transition temperature of the resin composition of the present invention is measured under the above-described measurement conditions 1, at least one of the three films with different thicknesses has a glass transition temperature of 200°C or higher. Here, it is speculated that when the glass transition temperature is 200°C or higher, the cyclization rate of the cyclized resin in the cured product is high. It is believed that because of this high cyclization rate, gas release caused by further cyclization in the film after curing can be suppressed.

[0391] The 2-hour heating in the above-described measurement condition 1 was carried out under a nitrogen atmosphere. The glass transfer temperature was determined by the method described in the examples.

[0392] Furthermore, under the above-described measurement conditions 1, a cyclization rate of 95% or higher for the cured material (the cured material before glass transfer temperature measurement) is preferred, 98% or higher is more preferred, and 99% or higher is even more preferred. There is no particular upper limit to the cyclization rate; it can be 100%. The cyclization rate is determined by the above method. It is believed that when the cyclization rate is within the above range, the movement (migration) of metal ions from the metal layer to the cured material via the uncyclized portion as the penetration path can be suppressed, resulting in a cured material with excellent adhesion to the metal.

[0393] The details of the components contained in the resin composition of the present invention, the characteristics of the resin composition, etc. are the same as those of the components contained in the resin composition used in the method for manufacturing the cured product of the present invention described above, and the preferred embodiment is also the same.

[0394] (Curing Compound) The curing compound of the present invention is a curing compound obtained by curing the resin composition of the present invention. The details of the curing compound of the present invention are the same as those of the curing compound obtained by the above-described method for manufacturing the curing compound of the present invention, and the preferred embodiment is also the same.

[0395] (Laminated body and method for manufacturing laminated body) The laminated system of the present invention refers to a structure having a plurality of layers composed of the curing material of the present invention. The laminated system of the present invention comprises a laminated body having two or more layers composed of curing material, and may also be a laminated body composed of three or more layers. Among the two or more layers composed of curing material included in the above-mentioned laminated body, at least one layer is composed of the curing material of the present invention. From the viewpoint of suppressing the shrinkage of the curing material or the deformation of the curing material that occurs with the shrinkage, it is also preferable that all the layers composed of curing material included in the above-mentioned laminated body are composed of the curing material of the present invention.

[0396] 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 the steps of repeating the method for manufacturing the laminate of the present invention a plurality of times.

[0397] The laminate of the present invention comprises two or more layers consisting of a cured material formed by curing a resin composition containing a cyclized resin precursor, wherein at least one of the layers consisting of the cured material is a layer consisting of the cured material of the present invention. Here, the configuration in which all the layers consisting of the cured material in the laminate are layers consisting of the cured material of the present invention is also one of the preferred configurations of the present invention. The laminate of the present invention comprises two or more layers consisting of a cured material, and it is preferable that any of the layers consisting of the cured material contains a metal layer between them. It is preferable that the metal layer is formed by the metal layer forming step. That is, it is preferable that the method for manufacturing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layers consisting of the cured material between the plurality of cured material manufacturing methods. The preferred configuration of the metal layer forming step is as described above. As an example of the aforementioned laminate, a laminate containing at least three layers sequentially laminated: a layer composed of a first cured material, a metal layer, and a layer composed of a second cured material is preferred. Preferably, both the layer composed of the first cured material and the layer composed of the second cured material are layers composed of the cured material of the present invention. The resin composition of the present invention used to form the layer composed of the first cured material and the resin composition of the present invention used to form the layer composed of the second 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.

[0398] <Lamination Step> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step includes performing at least one of the following steps sequentially on the surface of a pattern (resin layer) or a metal layer: (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step. It is possible to repeat at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. The lamination step may obviously and appropriately further include the aforementioned drying step, etc.

[0399] When performing a further deposition step after the deposition step, a surface activation treatment step may be performed after the above-mentioned exposure step, the above-mentioned heating step, or the above-mentioned metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details regarding the surface activation treatment will be explained later.

[0400] It is preferable to perform the above-described lamination steps 2 to 20 times, and more preferably 2 to 9 times. For example, a structure with 2 or more but less than 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure with 2 or more but less than 9 layers is even more preferred. The composition, shape, film thickness, etc. of each of the above layers can be the same or different.

[0401] In this invention, it is particularly preferred that, after the metal layer is formed, a hardened form (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, examples include repeating at least one of the following steps in sequence: (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, and (e) metal layer formation step, or repeating at least one of the following steps in sequence: (a) film formation step, (d) heating step, and post-development exposure step, and (e) metal layer formation step. By alternately performing the deposition step of the resin composition layer (resin ...

Claims

1. A method for manufacturing a hardened material, comprising: The film forming step involves applying a resin composition containing a cyclized resin precursor onto a substrate to form a film. The heating step involves heating the aforementioned film at a heating temperature below 180°C, resulting in a glass transfer temperature of 200°C or higher for the obtained cured material. The precursor of the aforementioned cyclized resin is a resin having at least one repeating unit represented by formula (2) and another repeating unit represented by formula (PAI-2). In formula (2), A1 and A2 independently represent oxygen atoms or -NRz-, R111 represents a divalent organic group, R115 is a group represented by formula (X1-3) or formula (X1-4) or a group comprising one or more aliphatic ring structures, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and Rz represents hydrogen atoms or monovalent organic groups. In formula (PAI-2), R117 is a group formed by any one of the groups represented in formulas (X2-1) to (X2-3) or a group containing one or more aliphatic ring structures; R111 represents a divalent organic group; A2 represents an oxygen atom or -NRz-; R113 represents a hydrogen atom or a monovalent organic group; Rz represents a hydrogen atom or a monovalent organic group. In formula (X1-3), R independently represents a substituent; m1 independently represents an integer from 0 to 2; L1 represents -CRC2- or -S(=O)2- or -O-; RC represents a monovalent organic group; * represents the bonding site with other structures. In formula (X2-1), R represents a substituent; n2 represents an integer from 0 to 2; * represents the bonding site with other structures. In formula (X2-2), R independently represents a substituent; m2 represents an integer from 0 to 3; m3 represents an integer from 0 to 4; * represents the bonding site with other structures. In formula (X2-3), R represents substituents independently, m2 represents integers from 0 to 2, m3 represents integers from 0 to 3, L2 represents -CRC2-, -S(=O)2- or -O-, RC represents a monovalent organic group, and * represents the bonding sites with other structures.

2. The method for manufacturing the hardened material as described in claim 1, wherein the aforementioned heating temperature is below 170°C.

3. The method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the film after the aforementioned heating step is a polyimide film containing polyimide, and the polyimide has an imidization rate of 90% or more.

4. The method for manufacturing a hardened material as described in claim 1 or claim 2, further comprising an exposure step of selectively exposing the aforementioned film between the aforementioned film formation step and the aforementioned heating step.

5. The method for manufacturing a hardened material as described in claim 4, further comprising, between the aforementioned exposure step and the aforementioned heating step, a developing step of developing the exposed film with a developing solution to form a pattern.

6. The method for manufacturing a hardened material as described in claim 5, wherein the aforementioned developing solution contains an organic solvent.

7. The method for manufacturing a hardened material as described in claim 5, wherein the aforementioned developing step is a step of forming a negative pattern.

8. The method for manufacturing a hardened material as described in claim 5, wherein the aforementioned developing solution contains an alkali.

9. The method for manufacturing a hardened material as claimed in claim 5, wherein between the aforementioned developing step and the aforementioned heating step, a processing step is included in which a treatment solution containing an alkali is brought into contact with the aforementioned pattern.

10. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned resin composition comprises a photosensitizer.

11. A method for manufacturing a cured product as described in claim 1 or claim 2, wherein the aforementioned resin composition contains a solvent, and the content of the precursor of the aforementioned cyclized resin is 70% by mass or more relative to the total solids content of the aforementioned resin composition.

12. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned resin composition comprises a polymeric compound having a boiling point of 200°C or higher at 1 atmosphere.

13. The method for manufacturing a hardened material as described in claim 12, wherein the polymeric compound having a boiling point of 200°C or higher at 1 atmosphere is a compound having 3 or more (meth)acrylate groups.

14. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned resin composition comprises a polymeric compound having an aliphatic ring structure.

15. A method for manufacturing a hardened compound as described in claim 1 or 2, wherein R111 in the aforementioned formula (2) is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group comprising one or more aliphatic ring structures, and R111 in the aforementioned formula (PAI-2) is a group represented by any one of the following formulas (W1-1) to (W1-3) or a group comprising one or more aliphatic ring structures, [Chemical Formula 3] In formula (W1-1), R represents a substituent, n1 represents an integer from 0 to 4, and * represents a bonding site with other structures, and in formula (W1-2), R independently represents a substituent, m4 independently represents an integer from 0 to 4, and * represents a bonding site with other structures. In formula (W1-3), R independently represents substituents, m4 independently represents integers from 0 to 3, L3 represents -CRC2- or -S(=O)2-, RC represents a monovalent organic group, and * represents the bonding site with other structures. In formula (W1-4), R independently represents substituents, n3 represents integers from 0 to 6, and * represents the bonding site with other structures. In formula (W1-5), R independently represents substituents, n4 independently represents integers from 0 to 3, X1 and X2 independently represent oxygen atoms, -S(=O)2- or -CRC2-, RC independently represent hydrogen atoms or monovalent organic groups, and * represents the bonding site with other structures.

16. A method for manufacturing a cured product as claimed in claim 1 or 2, wherein the precursor of the aforementioned cyclized resin satisfies condition 1 when it does not contain a repeating unit represented by formula (PAI-2), condition 2 when it does not contain a repeating unit represented by formula (2), and at least one of conditions 1 and 2 when it contains both a repeating unit represented by formula (2) and a repeating unit represented by formula (PAI-2): Condition 1: The precursor of the aforementioned cyclized resin contains a repeating unit of at least one of -A2-R113 and -A1-R114 in formula (2) that is a group represented by formula (3-1); Condition 2: The precursor of the aforementioned cyclized resin contains a repeating unit of -A2-R113 in formula (PAI-2) that is a group represented by formula (3-1); [Chemical Formula 4] In formula (3-1), Z1 and Z2 represent organic groups independently. Z1 and Z2 can be bonded to form a ring structure. * indicates the bonding site with other structures.

17. A method of manufacturing a laminate, comprising repeatedly manufacturing a hardened material according to any one of claims 1 to 16.

18. A method for manufacturing a semiconductor device, comprising a method for manufacturing a cured material as described in any one of claims 1 to 16 or a method for manufacturing a multilayer as described in claim 17.

19. A resin composition comprising a precursor of a cyclized resin, wherein, when measuring the glass transition temperature under the following measurement condition 1, at least one of three films of different thicknesses has a glass transition temperature of 200°C or higher, wherein measurement condition 1: the aforementioned resin composition is coated on a silicon substrate with thicknesses of 5 μm, 10 μm, or 20 μm, dried at 100°C for 5 minutes, and then cured by heating at 180°C for 2 hours; the glass transition temperature of the cured material cooled to 25°C is measured using a differential scanning calorimeter, wherein... The precursor of the aforementioned cyclized resin is a resin having at least one repeating unit represented by formula (2) and a repeating unit represented by formula (PAI-2). In formula (2), A1 and A2 independently represent an oxygen atom or -NRz-, R111 represents a divalent organic group, R115 is a group represented by formula (X1-3) or formula (X1-4) or a group containing one or more aliphatic ring structures, R113 and R114 independently represent a hydrogen atom or a monovalent organic group, and Rz represents a hydrogen atom or a monovalent organic group. In formula (PAI-2), R117 is a group represented by any one of formulas (X2-1) to (X2-3) or a group containing one or more aliphatic ring structures, R111 represents a divalent organic group, A2 represents an oxygen atom or -NRz-, R113 represents a hydrogen atom or a monovalent organic group, and Rz represents a hydrogen atom or a monovalent organic group. In formula (X1-3), R independently represents a substituent, m1 independently represents an integer from 0 to 2, L1 represents -CRC2- or -S(=O)2- or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures. In formula (X2-1), R represents a substituent, n2 represents an integer from 0 to 2, and * represents the bonding site with other structures. In formula (X2-2), R independently represents a substituent, m2 represents an integer from 0 to 3, m3 represents an integer from 0 to 4, and * represents the bonding site with other structures. In formula (X2-3), R independently represents a substituent, m2 represents an integer from 0 to 2, m3 represents an integer from 0 to 3, L2 represents -CRC2-, -S(=O)2- or -O-, RC represents a monovalent organic group, and * represents the bonding site with other structures.

20. A hardened material formed by hardening the resin composition described in claim 19.

21. A laminate comprising two or more layers of a cured material formed by curing a resin composition comprising a precursor of a cyclized resin, wherein at least one of the layers of the cured material is a layer of the cured material described in claim 20.

22. A semiconductor device comprising the hardened material of claim 20 or the laminate of claim 21.