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

Abstract

Provided are: a resin composition including a polyimide or a polyimide precursor, wherein a cured product obtained from the resin composition satisfies all of the following conditions (i) to (iv); a cured product; a laminate; a method for producing cured product; a method for producing a laminate; a method for producing a semiconductor device; and a semiconductor device; condition (i): Young's modulus of the cured product is 3.5 GPa or more, condition (ii): the coefficient of thermal expansion of the cured product in the temperature range from 25°C up to 125°C is less than 50 ppm / °C, condition (iii): the Tg of the cured product is 240°C or higher, and condition (iv): the elongation at break of the cured product is 40% or higher.

Description

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

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

[0002] In modern times, resin materials produced from resin compositions containing resins are being utilized in various fields. For example, polyimides are used in a variety of applications due to their excellent heat resistance and insulating properties. Examples of such applications include, but are not limited to, insulating films, encapsulants, and protective films for semiconductor devices used for packaging. Polyimides are also used as base films and coverlays for flexible substrates.

[0003] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing polyimide or a polyimide precursor. Such a resin composition can be applied to a substrate, for example, by coating, to form a photosensitive film, and then, as necessary, by performing exposure, development, heating, etc., to form a cured product on the substrate. The polyimide precursor is cyclized, for example, by heating, to form a polyimide in the cured product. Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, for example, a high degree of design freedom in the shape, size, application position, etc., of the applied resin composition. In addition to the high performance of polyimide, from the perspective of such excellent manufacturing adaptability, the industrial application development of the above-mentioned resin composition is increasingly expected.

[0004] Patent Document 1 describes a resin composition comprising (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a photopolymerizable substance, and (D) a solvent, wherein the polyimide precursor has a specific structure, and the (D) solvent is selected from at least one of γ-butyrolactone, dimethyl sulfoxide, and 3-methoxy-N,N-dimethylpropionamide, and wherein the resin composition has a development time increase rate of 130% or more but less than 200%, as expressed by the following mathematical formula (S1): Development time increase rate (%)=(DT48 / DT2)×100 (S1) (where DT2 and DT48 represent the times required for the resin composition to be completely dissolved in cyclopentanone as a developer at 23°C after being coated on a silicon wafer and baked at 110°C for 240 seconds and then left to stand for 2 hours and 48 hours, respectively. Note that in the coating process, the film thickness after baking is 10.5 μm.)

[0005] Japanese Patent Application Laid-Open No. 2021-173787

[0006] Resin compositions for producing cured products are required to have excellent TCT (Thermal Cycle Test) crack resistance in the cured products obtained from these compositions. Excellent TCT crack resistance means that cracks are unlikely to occur between the cured product and the substrate even after a severe TCT test (e.g., 1000 cycles of temperatures between −55°C and 200°C).

[0007] The present invention aims to provide a resin composition that can give a cured product having excellent TCT crack resistance, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate.

[0008] Representative embodiments of the present invention are shown below. <1> A resin composition comprising a polyimide or a polyimide precursor, wherein the resin composition is heated at 230°C for 3 hours to produce a 15 μm-thick film-like cured product, which satisfies all of the following conditions (i) to (iv): Condition (i): The cured product has a Young's modulus of 3.5 GPa or more; Condition (ii): The cured product has a thermal expansion coefficient of less than 50 ppm / °C in the temperature range of 25°C to 125°C; Condition (iii): The cured product has a glass transition temperature of 240°C or more; and Condition (iv): The cured product has an elongation at break of 40% or more. <2> The resin composition according to <1>, wherein the cured product satisfies all of the following conditions (v) to (viii). Condition (v): The Young's modulus of the cured product is 4.5 GPa or more. Condition (vi): The thermal expansion coefficient of the cured product in the temperature range of 25°C to 125°C is less than 40 ppm / °C. Condition (vii): The glass transition temperature of the cured product is 260°C or more. Condition (viii): The breaking elongation of the cured product is 50% or more. <3> The resin composition according to <1> or <2>, further comprising a metal complex having a π-conjugated moiety containing a nitrogen atom. <4> The resin composition according to any one of <1> to <3>, wherein the polyimide precursor comprises a repeating unit represented by the following formula (1): In formula (1), Z １ is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, and Y １ is a divalent organic group, and A １ and A ２ are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ <5> A resin composition comprising: a polyimide precursor having a repeating unit represented by the following formula (1); and a metal complex having a π-conjugated moiety containing a nitrogen atom, wherein at least one of the repeating units is a monovalent organic group having an ethylenically unsaturated bond: In formula (1), Z １is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, and Y １ is a divalent organic group, and A １ and A ２ are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of Z in the formula (1) is a monovalent organic group having an ethylenically unsaturated bond. １ is a group represented by the following formula (a) or formula (b): In formula (a), R ａ１ each independently represents a monovalent group, m1 represents an integer of 0 to 3, R ａ２ each independently represents a monovalent group, m2 represents an integer of 0 to 4, R ａ３ each independently represents a monovalent group, m3 represents an integer of 0 to 3, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1). ｂ１ each independently represents a monovalent group, n1 represents an integer of 0 to 3, R ｂ２ each independently represents a monovalent group, n2 represents an integer of 0 to 4, R ｂ３ each independently represents a monovalent group, n3 represents an integer of 0 to 4, R ｂ４ each independently represents a monovalent group; n4 represents an integer of 0 to 3; J １ and J ２ each independently represents a hydrogen atom, an alkyl group, or a trifluoromethyl group, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1). １ is a divalent organic group represented by the following formula (Y-1): In formula (Y-1), R ４ ~R １１ are each independently a hydrogen atom or a monovalent group, and R ４ ~R １１At least one of R is an alkyl group, a fluorine atom, a trifluoromethyl group, or an alkoxy group; ６ and R ８ , R ７ and R ９ may bond to form a ring structure, and * represents a bonding site with the nitrogen atom in formula (1). <8> The resin composition according to <3> or <5>, wherein the metal complex includes a partial structure represented by the following formula (1-1) as the structure including the π-conjugated site containing the nitrogen atom: In formula (1-1), X １ ~X ３each independently represent -C(-*)= or -N=, * represents a bonding site with another structure, and # represents a bonding site with a metal atom. <9> The resin composition according to any one of <1> to <8>, wherein the weight-average molecular weight of the polyimide precursor is 40,000 or more. <10> The resin composition according to any one of <1> to <9>, further comprising a polymerizable compound and a photopolymerization initiator. <11> The resin composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a redistribution layer. <12> A cured product obtained by curing the resin composition according to any one of <1> to <11>. <13> A laminate comprising two or more layers made of the cured product according to <12>, and comprising a metal layer between any of the layers made of the cured product. <14> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <11> onto a substrate to form a film. <15> A method for producing the cured product according to <14>, comprising an exposure step of selectively exposing the film to light and a development step of developing the film using a developer to form a pattern. <16> A method for producing the cured product according to <14> or <15>, comprising a heating step of heating the film at 50 to 450°C. <17> A method for producing a laminate, comprising the method for producing a cured product according to any one of <14> to <16>. <18> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <14> to <16> or the method for producing the laminate according to <17>. <19> A semiconductor device, comprising the cured product according to <12> or the laminate according to <13>. <20> A cured product that satisfies all of the following conditions (i) to (iv): Condition (i): the Young's modulus of the cured product is 3.5 GPa or more; Condition (ii): the thermal expansion coefficient of the cured product in the temperature range of 25 to 125°C is less than 50 ppm / °C; Condition (iii): the glass transition temperature of the cured product is 240°C or more; and Condition (iv): the breaking elongation of the cured product is 40% or more. <21> A semiconductor device comprising: a semiconductor chip; and a rewiring layer, the rewiring layer including wiring and an interlayer insulating film for the rewiring layer that satisfies all of the following conditions (i) to (iv):Condition (i): The Young's modulus of the interlayer insulating film for redistribution layer is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the interlayer insulating film for redistribution layer in a temperature range of 25 to 125°C is less than 50 ppm / °C. Condition (iii): The glass transition temperature of the interlayer insulating film for redistribution layer is 240°C or more. Condition (iv): The breaking elongation of the interlayer insulating film for redistribution layer is 40% or more. <22> The semiconductor device according to <21>, further comprising a sealing material covering the semiconductor chip, wherein an area of ​​the redistribution layer in a planar view is larger than that of the semiconductor chip.

[0009] According to the present invention, there are provided a resin composition that can give a cured product having excellent TCT crack resistance, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate.

[0010] 1 is an example of a semiconductor device according to a second embodiment of the present invention.

[0011] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). 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. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights were measured using NMP (N-methyl-2-pyrrolidone) as the eluent. Furthermore, unless otherwise specified, detection in GPC measurements was performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower," it is sufficient that another layer is above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that such up-and-down directions are defined for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from the vertically upward direction. Unless otherwise specified in this specification, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified in this specification, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, combinations of preferred embodiments are more preferred embodiments.

[0012] (Resin Composition) The resin composition according to the first aspect of the present invention (hereinafter also referred to as "first resin composition") is a resin composition containing polyimide or a polyimide precursor, and a film-like cured product having a thickness of 15 μm obtained by heating the resin composition at 230° C. for 3 hours satisfies all of the following conditions (i) to (iv): Condition (i): The Young's modulus of the cured product is 3.5 GPa or more; Condition (ii): The thermal expansion coefficient of the cured product in the temperature range of 25 to 125° C. is less than 50 ppm / ° C.; Condition (iii): The glass transition temperature of the cured product is 240° C. or more; and Condition (iv): The breaking elongation of the cured product is 40% or more.

[0013] A resin composition according to a second aspect of the present invention (hereinafter also referred to as a "second resin composition") comprises a polyimide precursor containing a repeating unit represented by the following formula (1), and a metal complex having a π-conjugated moiety containing a nitrogen atom: In formula (1), Z １ is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, and Y １ is a divalent organic group, and A １ and A ２ are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond.

[0014] Hereinafter, the resin composition according to the first aspect of the present invention and the resin composition according to the second aspect of the present invention will be collectively referred to as "the resin composition of the present invention" or simply as "the resin composition."

[0015] The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. In particular, use of the resin composition of the present invention to form an interlayer insulating film for a redistribution layer is also a preferred embodiment of the present invention. The resin composition of the present invention is also preferably used to form a photosensitive film that is subjected to negative development. In the present invention, negative development refers to development in which unexposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. The exposure method, developer, and development method may, for example, be the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below.

[0016] The resin composition of the present invention provides a cured product having excellent TCT crack resistance. The mechanism by which this effect is achieved is unknown, but is presumed to be as follows.

[0017] The first resin composition of the present invention is a composition that can yield a cured product that satisfies all of the following characteristics: high Young's modulus, low CTE (low coefficient of thermal expansion), high Tg (high glass transition temperature), and high elongation at break. It has been found that the cured product obtained from such a first resin composition suppresses cracking even in a rigorous TCT test, demonstrating excellent reliability. It is believed that a high Young's modulus of the cured product results in high film strength, making it less likely to crack. It is believed that a low CTE of the cured product is closer to the CTE of the substrate, such as silicon or copper wiring, thereby reducing the difference in expansion coefficient with temperature change and making it less likely to crack. It is believed that a high Tg of the cured product suppresses changes in the composition of the cured product due to temperature changes, making it less likely for components volatilizing from the cured product to escape to the outside of the cured product, thereby preventing the occurrence of weak areas in the cured product and making it less likely to crack. It is believed that a high elongation at break allows the cured product itself to easily follow deformations of the substrate, wiring, etc., caused by temperature changes, making it less likely to crack. That is, it is presumed that a cured product with excellent TCT crack resistance can be obtained as a result of the synergistic effect of the four conditions of high Young's modulus, low CTE, high Tg, and high elongation at break.

[0018] The polyimide precursor contained in the second resin composition is represented by the formula (1) １ The second resin composition has a tetravalent organic group containing two or more ether groups and an aromatic ring structure at the position. Because the structure is flexible, the resulting cured product is thought to have excellent elongation at break (high elongation at break). Furthermore, the second resin composition contains a metal complex having a π-conjugated moiety containing a nitrogen atom. This further increases the glass transition temperature of the cured product and improves adhesion between the film and the substrate. Therefore, it is presumed that a cured product with excellent TCT crack resistance can be obtained.

[0019] However, Patent Document 1 does not describe either the first resin composition or the second resin composition of the present invention.

[0020] The resin composition of the present invention will be described in detail below.

[0021] <Conditions (i) to (iv)> A 15 μm thick film-like cured product obtained by heating the first resin composition of the present invention at 230° C. for 3 hours satisfies the following conditions (i) to (iv). A 15 μm thick film-like cured product obtained by heating the second resin composition of the present invention at 230° C. for 3 hours preferably satisfies the following conditions (i) to (iv). Condition (i): The Young's modulus of the cured product is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the cured product in the temperature range of 25° C. to 125° C. is less than 50 ppm / ° C.. Condition (iii): The glass transition temperature of the cured product is 240° C. or more. Condition (iv): The breaking elongation of the cured product is 40% or more.

[0022] Here, the film-like cured product having a thickness of 15 μm obtained by heating the resin composition of the present invention at 230° C. for 3 hours is preferably obtained by applying the resin composition of the present invention to a substrate to form a resin composition layer, and then heating it at 230° C. for 3 hours.

[0023] The substrate is preferably the substrate described in the method for producing a cured product of the present invention described later, for example, a silicon wafer. The method for applying the resin composition can be the application method described in the film formation step in the method for producing a cured product of the present invention described later, and from the viewpoint of easy thickness adjustment and easy uniformity of thickness, spin coating or slit coating is preferred, and spin coating is more preferred. The application method can be determined taking into account the viscosity of the resin composition, the physical properties of the components contained, etc.

[0024] The resin composition layer may be dried before heating. Examples of drying methods include the application methods described in the heating step in the method for producing a cured product of the present invention described below. In particular, when the resin composition contains a solvent, it is preferable to dry it before heating. The drying is preferably carried out at a temperature of, for example, 50 to 150°C. The temperature is more preferably 70 to 130°C, and even more preferably 90 to 110°C. For example, it can be carried out at 100°C. The drying may be carried out under reduced pressure, but is preferably carried out under atmospheric pressure. The drying means is not particularly limited, and for example, known heating means can be used, but it is preferable to use a hot plate.

[0025] The resin composition layer is cured by heating at 230°C for 3 hours. Examples of heating methods include those described in the drying step of the cured product manufacturing method of the present invention, which will be described later. The heating is preferably performed at a temperature increase rate of 1 to 12°C / min. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. For example, heating can be performed at 10°C / min. The heating can be performed in an atmosphere with an oxygen concentration of 100 ppm or less, for example, by flowing an inert gas such as nitrogen, helium, or argon, or by performing heating under reduced pressure. For example, heating can be performed in a nitrogen atmosphere with an oxygen concentration of 100 ppm or less. The heating means used in the heating step is not particularly limited, but examples include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven. For example, heating can be performed using an electric heating oven.

[0026] When the resin composition of the present invention is applied to a substrate to form a resin composition layer, the cured product obtained after the heating is preferably peeled off from the substrate. The peeling method is not particularly limited, but peeling is preferably performed by immersing the cured product and the substrate in an aqueous acid solution. For example, peeling can be performed by immersing the cured product and the substrate in a 4.9% by mass aqueous hydrofluoric acid solution.

[0027] The shape and size of the cured product are not particularly limited, but can be, for example, a dumbbell shape with a sample width of 2 mm and a sample length of 35 mm. The dumbbell shape can be, for example, a dumbbell No. 7 shape as described in JIS K 6251:2017. Furthermore, the resin composition may be subjected to exposure and development to obtain a cured product of a specific shape and size. The exposure method and development method may be determined depending on the composition, and examples include the exposure method and development method described in the exposure step and development step in the method for producing a cured product of the present invention described below. It is also preferable to obtain a cured product of the desired shape and size by punching using a punching tool or the like.

[0028] Under the condition (i), the Young's modulus of the cured product is preferably 4.0 GPa or more, more preferably 4.5 GPa or more. The upper limit of the Young's modulus is not particularly limited, but is preferably 6.5 GPa or less. The Young's modulus can be measured according to the method of JIS (Japanese Industrial Standards)-K7161-1 (2014). The Young's modulus can be measured, for example, in an environment of 25°C and 65% RH (relative humidity). The Young's modulus can also be measured using a known dynamic viscoelasticity measuring device or a similar device. An example of such a device is the DMA850 (TA Instruments). The test speed (crosshead speed) when measuring the Young's modulus can be, for example, 5 mm / min. The Young's modulus can also be measured, for example, by the method described in the Examples below.

[0029] Under the condition (ii), the coefficient of thermal expansion (CTE) of the cured product in the temperature range of 25°C to 125°C is preferably less than 45 ppm / °C, more preferably less than 40 ppm / °C. The lower limit of the CTE is not particularly limited, but is preferably 15 ppm / °C or higher. The CTE can be measured using a known thermomechanical analyzer, a thermal expansion coefficient measuring device, or a similar device. An example of such a device is the TMA450 (TA Instruments). The heating and cooling conditions during evaluation can be, for example, as follows (1) to (4): (1) Heat from room temperature to 130°C at a heating rate of 5°C / min; (2) Cool from 130°C to 10°C at a cooling rate of 5°C / min; (3) Heat from 10°C to 220°C at a heating rate of 5°C / min; (4) Allow to cool naturally to room temperature. The elongation (displacement) of the sample is measured during the temperature increase and decrease processes (1) to (4) above, and the thermal expansion coefficient is calculated by dividing the elongation (displacement) of the sample at 25°C and 125°C in process (3) by the temperature. (For example, if the length of the sample at 25°C is 50 mm and the length of the sample at 125°C is 50.2 mm, the displacement is calculated as 0.4% = 4000 ppm, and the thermal expansion coefficient is calculated as 4000 / (125-25) = 40 ppm / °C.) The thermal expansion coefficient can be measured by the method described in the examples below.

[0030] Under the above condition (iii), the glass transition temperature (Tg) of the cured product is preferably 250°C or higher, more preferably 260°C or higher. The upper limit of the glass transition temperature is not particularly limited, but is preferably 350°C or lower, for example. The glass transition temperature can be measured using a known thermomechanical analyzer, thermal expansion analyzer, or similar device. An example of such a device is the DMA850 (TA Instruments). Specifically, the glass transition temperature is measured by changing the temperature conditions of the cured product in the following order (1) to (2): (1) Raise the temperature from 25°C to 350°C at a rate of 5°C / min; (2) Cool from 350°C to 25°C. The glass transition temperature can also be measured by the method described in the Examples below.

[0031] Under the condition (iv), the breaking elongation of the cured product is preferably 45% or more, more preferably 50% or more. The upper limit of the breaking elongation is not particularly limited, but is preferably 150% or less, for example. The breaking elongation can be measured according to the method of JIS-K7161-1 (2014). The breaking elongation can be measured, for example, in an environment of 25°C and 65% RH (relative humidity). The breaking elongation can be measured using a known tensile tester or a similar device. An example of such a device is a tensile tester (Instron Model 5965). The test speed (crosshead speed) when measuring the breaking elongation can be, for example, 5 mm / min. The breaking elongation is measured by the method described in the Examples below.

[0032] Here, it is preferable that the cured product in the form of a film having a thickness of 15 μm obtained by heating the resin composition of the present invention at 230° C. for 3 hours satisfies the following conditions (v) to (viii): Condition (v): The Young's modulus of the cured product is 4.5 GPa or more; Condition (vi): The thermal expansion coefficient of the cured product in the temperature range of 25° C. to 125° C. is less than 40 ppm / ° C.; Condition (vii): The glass transition temperature of the cured product is 260° C. or more; and Condition (viii): The breaking elongation of the cured product is 50% or more.

[0033] <Polyimide or Polyimide Precursor> The first resin composition of the present invention contains a polyimide or a polyimide precursor, and preferably contains a polyimide precursor. The polyimide precursor preferably contains a repeating unit represented by the following formula (1). The polyimide preferably contains a repeating unit represented by formula (P1) described below. The second resin composition of the present invention contains a polyimide precursor containing a repeating unit represented by the following formula (1). Hereinafter, polyimide and polyimide precursor will also be collectively referred to as a "specific resin." In formula (1), Z １ is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, and Y １ is a divalent organic group, and A １ and A ２are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond.

[0034] [A １ and A ２ A in formula (1) １ and A ２ are each independently an oxygen atom or —NR Ｚ -, and an oxygen atom is preferred. Ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. Ｚ is a monovalent organic group, Ｚ Examples of the alkyl group include hydrocarbon groups. １ Ga-NR Ｚ -, then R Ｚ is R １ A may be bonded to form a ring structure. Examples of the ring structure that is formed include a hydrocarbon ring, preferably an aliphatic hydrocarbon ring, and more preferably a saturated aliphatic hydrocarbon ring. The ring structure is preferably a 5-membered ring or a 6-membered ring. ２ Ga-NR Ｚ -, then R Ｚ is R ２ A preferred embodiment of the ring structure formed is Ｚ and R １ The preferred embodiments are the same as those of the ring structure formed by bonding with

[0035] [R １ and R ２ ] In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of R is a monovalent organic group having an ethylenically unsaturated bond. １ and R ２and (III) are monovalent organic groups having an ethylenically unsaturated bond is also a preferred embodiment of the present invention. The monovalent organic group having an ethylenically unsaturated bond is preferably a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a group having a (meth)acryloyloxy group, or a group having a group represented by formula (III) below, and more preferably a group having a group represented by formula (III) below. Furthermore, an embodiment in which the monovalent organic group having an ethylenically unsaturated bond is a group represented by formula (III) below is also a preferred embodiment of the present invention.

[0036]

[0037] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0038] In formula (1), R １is a hydrogen atom, or R ２ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0039] In formula (1), R １ and R ２ The monovalent organic group having no ethylenically unsaturated bond may be a hydrocarbon group, a heterocyclic group, or a combination of at least one of a hydrocarbon group and a heterocyclic group and —O—, —C(═O)—, —S—, or —SO ２ -or-NR Ｎ A group represented by a combination of R and - is preferred, a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O- is more preferred, and an alkyl group, an aromatic hydrocarbon group or a polyalkyleneoxy group is more preferred. Ｎ represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a hydrocarbon group, or an aromatic group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. In this specification, when simply referring to an alkyl group, the alkyl group includes any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. The same applies to alkylene groups, aliphatic hydrocarbon groups, etc.

[0040] [Z １ ] In formula (1), Z １ is a tetravalent organic group containing two or more ether groups and an aromatic ring structure. Here, the ether group is a divalent group represented by *-O-*, and both *s are groups that bond to hydrocarbon groups. Z １In the present invention, the two ether groups in Z are directly bonded at both ends to the aromatic ring structure, which is also a preferred embodiment of the present invention. In the present invention, "A and B are directly bonded" means that A and B are bonded without a linking group between A and B. １ The number of ether groups in the formula (I) is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The ether bond is preferably present on the main chain of the resin. In the present invention, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to any other bonding chain. In the present invention, the term "a certain structure is present on the main chain" means that the main chain is connected by the certain structure, and removing the certain structure would result in the main chain being severed.

[0041] Z １ The aromatic ring structure in may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure, but is preferably an aromatic hydrocarbon ring structure. The aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring structure having 6 to 10 carbon atoms, and even more preferably a benzene ring structure. The aromatic heterocyclic structure is preferably a 5-membered ring structure, a 6-membered ring structure, or a ring structure represented by a combination thereof, and more preferably a 6-membered ring structure. Examples of heteroatoms in the aromatic heterocyclic structure include an oxygen atom, a nitrogen atom, and a sulfur atom. In addition, Z １ The number of benzene ring structures contained in Z is preferably 1 to 6, and more preferably 1 to 4. １ It is also preferable that the aromatic ring structure has three or more benzene ring structures. In the above embodiment, the number of benzene ring structures is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 or 4. The aromatic ring structure may have a known substituent. Examples of the substituent include an alkyl group, a halogen atom, and an alkyl group in which a hydrogen atom is substituted with a halogen atom. The aromatic ring structure is preferably present on the main chain of the resin.

[0042] Z １is preferably a structure represented by the following formula (a) or (b): In formula (a), R ａ１ each independently represents a monovalent group, m1 represents an integer of 0 to 3, R ａ２ each independently represents a monovalent group, m2 represents an integer of 0 to 4, R ａ３ each independently represents a monovalent group, m3 represents an integer of 0 to 3, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1). ｂ１ each independently represents a monovalent group, n1 represents an integer of 0 to 3, R ｂ２ each independently represents a monovalent group, n2 represents an integer of 0 to 4, R ｂ３ each independently represents a monovalent group, n3 represents an integer of 0 to 4, R ｂ４ each independently represents a monovalent group; n4 represents an integer of 0 to 3; J １ and J ２ each independently represents a hydrogen atom, an alkyl group, or a trifluoromethyl group, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1).

[0043] In formula (a), R ａ１ is preferably a halogen atom, an aliphatic hydrocarbon group, or an aromatic group. The hydrogen atom in the aliphatic hydrocarbon group or aromatic group may be further substituted with a halogen atom or the like. In formula (a), m1 represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1. An embodiment in which m1 is 0 is also one of the preferred embodiments of the present invention. In formula (a), R ａ２ and R ａ３ A preferred embodiment of R ａ１ In formula (a), m2 is preferably 0 to 2, and more preferably 0 or 1. An embodiment in which m2 is 0 is also one of the preferred embodiments of the present invention. In formula (a), the preferred embodiment of m3 is the same as the preferred embodiment of m1. In formula (a), one of *1 and *2 is A in formula (1), １one of *3 and *4 is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and the other is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and one of *3 and *4 is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and ２ and the other preferably binds to a carbonyl group bonded to NH described in formula (1).

[0044] In formula (b), R ｂ１ is preferably a halogen atom, an aliphatic hydrocarbon group, or an aromatic group. The hydrogen atoms in the aliphatic hydrocarbon group or aromatic group may be further substituted with a halogen atom or the like. In formula (b), n1 represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. In formula (b), R ｂ２ , R ｂ３ and R ｂ４ A preferred embodiment of R ｂ１ In formula (b), n2 is preferably 0 to 2, and more preferably 0 or 1. An embodiment in which n2 is 0 is also one of the preferred embodiments of the present invention. In formula (b), the preferred embodiment of n3 is the same as the preferred embodiment of n2. In formula (b), the preferred embodiment of n4 is the same as the preferred embodiment of n1. In formula (b), J １ and J ２ each independently represents a hydrogen atom, an alkyl group, or a trifluoromethyl group, and preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. １ one of *3 and *4 is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and the other is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and one of *3 and *4 is a carbonyl group bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (1), and ２ and the other preferably binds to a carbonyl group bonded to NH described in formula (1).

[0045] [Y １ 〕 Y １ is preferably a divalent organic group represented by formula (Y-1). In formula (Y-1), R ４ ~R１１ At least one of R is an alkyl group, a fluorine atom, a trifluoromethyl group, or an alkoxy group; ６ and R ８ , R ７ and R ９ may bond to form a ring structure, and * represents the bonding site with the nitrogen atom in formula (1). ４ ~R １１ At least one of R is preferably a fluorine atom or a trifluoromethyl group, since these groups have excellent solvent solubility and small i-line absorption, thereby enabling high resolution. ４ ~R １１ Preferably, at least two of the groups in formula (Y-1)R are alkyl groups, fluorine atoms, or trifluoromethyl groups. The alkyl groups are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. The alkoxy groups are preferably alkoxy groups having 1 to 4 carbon atoms, and more preferably methoxy groups. In addition, in formula (Y-1)R ６ and R ８ , R ７ and R ９ may be bonded to form a ring structure. The ring structure formed is not particularly limited, but a hydrocarbon ring is preferred. The ring structure formed is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure. Y １ is also preferably a divalent organic group represented by formula (Y-2). In formula (Y-2), R ５ and R ８ are each independently an alkyl group, a fluorine atom, or a trifluoromethyl group, and * represents a bonding site with the nitrogen atom in formula (1). In formula (Y-2), R ５ and R ８ are each preferably independently a fluorine atom or a trifluoromethyl group. ５ and R ８ The alkyl group in is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

[0046] Specific examples of the divalent organic group represented by formula (Y-1) include structures represented by the following formulae, but the present invention is not limited to these. In the following formulae, * has the same meaning as * in formula (Y-1).

[0047] Also, Y １ is also preferably a group represented by formula (Y-3). In a particularly preferred embodiment, the polyimide precursor is １ A repeating unit represented by formula (Y-1) and Y １ and a repeating unit represented by formula (Y-2). In formula (Y-3), R １２ ~R １５ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and * represents a bonding site with the nitrogen atom in formula (1). １２ ~R １５ In one preferred embodiment of the present invention, all of R are hydrogen atoms. １２ ~R １５ The halogen atom in formula (Y-3) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom. １２ ~R １５ Examples of the monovalent organic group in the formula (I) include a hydrocarbon group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a poly(alkyleneoxy) group, a poly(aryleneoxy) group, a poly(alkyleneoxycarbonyl) group, a poly(aryleneoxycarbonyl) group, a hydroxy group, and a cyano group.

[0048] Others, Y １ is R in formula (2) described later. １１１ It may have a similar structure.

[0049] From the viewpoints of CTE, Tg, and Young's modulus, it is preferable that the polyimide precursor further contains a repeating unit represented by the following formula (3). In formula (3), Z２ is a tetravalent organic group represented by any one of the following formulas (2a) to (2d), and Y ２ is a divalent organic group, and A １ and A ２ are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond. ２ is preferably a tetravalent organic group represented by formula (2a) or formula (2d), and more preferably a tetravalent organic group represented by formula (2a). In formulas (2a) to (2d), L １ and L ２ are each independently a divalent group that is not conjugated with the benzene ring to which it is bonded, or a single bond, and *1 to *4 each represent a bonding site with the carbonyl group in formula (3).

[0050] In formula (2c), L １ and L ２ are each independently -C(R Ｃ ) ２ -, -Si(R Ｓ ) ２ -, -O-, or a single bond is preferred, and -C(R Ｃ ) ２ -, -Si(R Ｓ ) ２ It is more preferable that L is - or -O-. １ and L ２ At least one of the groups is -C(R Ｃ ) ２ - or -Si(R Ｓ ) ２ - is preferred. Ｃ are each independently a hydrogen atom or a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. Ｃmay be bonded to form a ring structure. Ｓ are each independently a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. Ｓ In formulas (2a) to (2d), either *1 or *2 may be bonded to A in formula (3). １ and the other bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (3), and one of *3 or *4 is A in formula (3). ２ and the other bonded to a carbonyl group bonded to NH described in formula (3). In addition, the hydrogen atoms in the ring structures described in formulas (2a) to (2d) may be substituted with known substituents. Examples of the substituent include alkyl groups, halogen atoms, and alkyl groups in which hydrogen atoms are substituted with halogen atoms.

[0051] Specific examples of the groups represented by formulae (2a) to (2d) include the following structures, but the present invention is not limited to these. In the structures below, *1 to *4 have the same meanings as *1 to *4 in formulae (2a) to (2d), respectively.

[0052] In formula (3), Y ２ , A １ , A ２ , R １ and R ２ A preferred embodiment of the formula is Y １ , A １ , A ２ , R １ and R ２ This is the same as the preferred embodiment of the above.

[0053] The polyimide precursor may further contain a repeating unit represented by the following formula (2) as a repeating unit different from both the repeating unit represented by the above formula (1) and the repeating unit represented by the formula (3). In other words, neither the repeating unit represented by the formula (1) nor the repeating unit represented by the formula (3) corresponds to the repeating unit represented by the following formula (2). In formula (2), A １ and A ２ are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚ represents a hydrogen atom or a monovalent organic group.

[0054] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１ represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. R in formula (2) １１１ Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred, where each Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0055] R １１１is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, R １１１ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0056] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents a bonding site to another structure.

[0057] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3 ,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane parafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl can be mentioned.

[0058] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0059] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0060] R １１１ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film, wherein each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0061] Also, R １１１From the viewpoint of i-line transmittance, it is preferable that is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of R is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0062] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. In formula (5), R １１２ represents a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２-, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0063] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５ The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of R in formula (2) is １１５ The same applies to the preferred range.

[0064] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0065] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0066] In formula (2), R １１１ and R １１５ At least one of R may have an OH group. １１１Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0067] R in formula (2) １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. １１３ and R １１４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１３ and R １１４ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the above formula (III), with the group represented by the above formula (III) being preferred.

[0068] In formula (2), R １１３ is a hydrogen atom, or R １１４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0069] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0070] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0071] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ each independently represents a divalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R １１３ and R １１４ At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0072] A １ , A ２ , R １１１ , R １１３ and R １１４ are each independently A in formula (2). １ , A ２ , R １１１ , R １１３ and R １１４ The same definition and preferred range are also true. １１２ is R in formula (5). １１２ The same applies to the preferred range.

[0073] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0074] The polyimide precursor may further contain other repeating units different from the repeating units represented by formulas (1) to (3). Examples of other repeating units include the repeating unit represented by formula (PAI-2) below. In formula (PAI-2), R １１７ represents a trivalent organic group, R １１１ represents a divalent organic group, A ２ represents an oxygen atom or —NH—, R １１３ represents a hydrogen atom or a monovalent organic group.

[0075] In formula (PAI-2), R １１７ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0076] Also, R １１７ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups in the tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and are used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0077] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0078] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are bonded with a single bond, —O—, —CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -SO ２ These compounds may be compounds in which two carboxy groups are anhydride (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0079] In formula (PAI-2), R １１１ , A ２ , R １１３ are R in the above formula (2), １１１ , A ２ , R １１３ The same applies to the preferred embodiments.

[0080] In one embodiment of the polyimide precursor, the content of the repeating units represented by formula (1) and the repeating units represented by formula (3) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (1), or may be repeating units represented by formula (1) and repeating units represented by formula (3). When the polyimide precursor contains repeating units represented by formula (1) and repeating units represented by formula (3), the content of the repeating units represented by formula (1) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, relative to the total molar content of the repeating units represented by formula (1) and the repeating units represented by formula (3).

[0081] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 40,000 or more. The weight-average molecular weight (Mw) of the polyimide precursor is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 10,000 to 40,000. The molecular weight dispersity of the polyimide precursor is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. The lower limit of the dispersity is not particularly limited, and may be 1.0 or more. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple polyimide precursors, 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 by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

[0082] [Polyimide] The polyimide contained in the first resin composition of the present invention includes a polyimide containing a repeating unit represented by the following formula (CR-1). In formula (CR-1), Z １ is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, and Y １ is a divalent organic group. １ and Y １ A preferred embodiment of the formula (1) is Z １ and Y １ This is the same as the preferred embodiment of the above.

[0083] The polyimide preferably further contains a repeating unit represented by the following formula (CR-3): In formula (CR-3), Z ２ is a tetravalent organic group represented by any one of the above formulas (2a) to (2d), and Y ２ is a divalent organic group. ２ and Y ２ A preferred embodiment of the formula (3) is Z ２ and Y ２ This is the same as the preferred embodiment of the above.

[0084] The polyimide may further contain a repeating unit represented by the following formula (CR-2) as a repeating unit different from both the repeating unit represented by the above formula (CR-1) and the repeating unit represented by the formula (CR-3). In other words, neither the repeating unit represented by the formula (CR-1) nor the repeating unit represented by the formula (CR-3) corresponds to the repeating unit represented by the following formula (CR-2). In formula (CR-2), R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group. １１１ and R １１５ A preferred embodiment of the formula (2) is １１１ and R １１５ This is the same as the preferred embodiment of the above. In formula (CR-4), R １１７represents a trivalent organic group, R １１１ represents a divalent organic group. １１１ and R １１７ A preferred embodiment of the formula (PAI-2) is R １１１ and R １１７ This is the same as the preferred embodiment of the above.

[0085] The polyimide preferably has a ring-closed structure of a polyimide precursor corresponding to the above-mentioned specific resin. That is, the polyimide may further contain a repeating unit represented by formula (1) to formula (3) or formula (PAI-1) contained in the polyimide precursor corresponding to the above-mentioned specific resin, or a repeating unit represented by formula (1) to formula (3) that is partially ring-closed.

[0086] From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the ring closure rate (imidization rate) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the imidization rate is not particularly limited, and it is sufficient as long as it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the absorption peak at 1377 cm －１ Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P1 around 1377cm. －１ The peak intensity P2 around the peak intensity P1 is measured. The imidization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0087] In one embodiment of the polyimide precursor, the content of the repeating units represented by formula (CR-1) and the repeating units represented by formula (CR-3) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal repeating units may be repeating units represented by formula (CR-1), or may be repeating units represented by formula (CR-1) and repeating units represented by formula (CR-3). When the polyimide precursor contains repeating units represented by formula (CR-1) and repeating units represented by formula (CR-3), the content of the repeating units represented by formula (CR-1) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, relative to the total molar content of the repeating units represented by formula (CR-1) and the repeating units represented by formula (CR-3).

[0088] The polyimide preferably contains fluorine atoms. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5 mass % or more and 20 mass % or less. In addition, the polyimide may contain silicon atoms.

[0089] It is also preferable that the polyimide contains a polymerizable group. Examples of the polymerizable group include, but are not limited to, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, and the like, with the group containing an ethylenically unsaturated bond being preferred. The ethylenically unsaturated bond preferably has radical polymerizability. Examples of the group containing an ethylenically unsaturated bond include a group containing an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group. The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The polymerizable group is, for example, R in the repeating unit represented by the above formula (CR-2). １１１ or R １１５ can be introduced into

[0090] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 40,000 or more. The weight-average molecular weight (Mw) of the polyimide is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 50,000, more preferably 3,000 to 40,000, and even more preferably 10,000 to 30,000. The molecular weight dispersity of the polyimide is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. The lower limit of the dispersity is not particularly limited, and it may be 1.0 or more. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple polyimides, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the multiple polyimides as a single resin are within the above-mentioned ranges.

[0091] The polyimide preferably contains fluorine atoms in its structure, and the fluorine atom content in the polyimide is preferably 10% by mass or more and 20% by mass or less.

[0092] [Method for Producing Polyimide Precursor or Polyimide] Polyimide precursors or polyimides can be synthesized, for example, by the methods described in the Examples below, but are not limited thereto. Specifically, polyimide precursors or polyimides can be obtained by, for example, reacting a tetracarboxylic dianhydride with a diamine at low temperature; reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, followed by esterification using a condensing agent or alkylating agent; obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by reaction with a diamine in the presence of a condensing agent; or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by acid-halogenating the remaining dicarboxylic acid with a halogenating agent, followed by reaction with a diamine. Among these production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by acid-halogenating the remaining dicarboxylic acid with a halogenating agent, followed by reaction with a diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. The organic solvent can be appropriately determined depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.The basic compound may be one kind or two or more kinds. The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0093] -End-capping agent- In order to further improve storage stability during the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and in terms of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0094] -Solid Precipitation- The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is poured into a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor or the like. To improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0095] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0096] <Other Resins> The resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include polybenzoxazole precursors, polyamideimide precursors, polyimides, polybenzoxazoles, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a polymerizable compound having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0097] When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. The content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0098] <Specific Metal Complex> The first resin composition of the present invention preferably contains a metal complex having a π-conjugated moiety containing a nitrogen atom (also referred to as a "specific metal complex"). The second resin composition of the present invention contains the specific metal complex.

[0099] [Metal Atoms] The type of metal atom contained in the specific metal complex is not particularly limited, but is preferably a Group 4 metal atom, more preferably a titanium atom, zirconium atom, or hafnium atom, and even more preferably a titanium atom from the viewpoint of storage stability. This is presumably because the titanium atom has a small atomic radius, which improves the stability of the compound. The number of metal atoms contained in the specific metal complex is not particularly limited, but may be 1 or more, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1. Furthermore, when the specific metal complex contains two or more of the above metal atoms, the types of the metal atoms may be the same or different. For example, when the specific metal complex contains two of the above metal atoms, it may contain two titanium atoms, or it may contain a titanium atom and a zirconium atom.

[0100] [π-conjugated moiety containing a nitrogen atom] The specific metal complex has a π-conjugated moiety containing a nitrogen atom. Here, the nitrogen atom is preferably directly bonded to a metal atom in the specific metal complex. The bond is not particularly limited, but is preferably a coordinate bond. Furthermore, the π-conjugated moiety may have only one nitrogen atom or may have two or more nitrogen atoms. When two or more nitrogen atoms are present, it is preferable that one of them is directly bonded to a metal atom in the specific metal complex. Here, the specific metal complex may have only one or two π-conjugated moieties containing a nitrogen atom, but it is preferable that it has one or two.

[0101] The π-conjugated moiety containing a nitrogen atom preferably has a structure represented by the following formula (1-1). In formula (1-1), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0102] In formula (1-1), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0103] In formula (1-1), at least two structures bonded to * may be bonded to form a ring structure.

[0104] The specific metal complex is preferably a compound having a π-conjugated moiety containing a nitrogen atom and at least one group selected from the group consisting of a hydroxy group, a mercapto group, and a carboxy group on the same ligand, wherein the hydroxy group, the mercapto group, and the carboxy group are preferably bonded to the metal atom as -O-, -S-, or -C(=O)-.

[0105] The specific metal complex may further have another structure different from the π-conjugated moiety containing a nitrogen atom. The other structure is not particularly limited, and a structure consisting of a known ligand can be used. Examples of the ligand include a monodentate alkoxide ligand, a monodentate aryloxide ligand, a multidentate aryloxide ligand, and a cyclopentadienyl ligand, and these ligands may further have a substituent. From the viewpoint of the stability of the specific metal complex, a substituted or unsubstituted cyclopentadienyl ligand is preferred.

[0106] The specific metal complex is preferably a compound represented by the following formula (2-1). In formula (2-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ is a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (2-2), and R ３ are each independently a group containing a structure represented by the following formula (2-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (2-2), X １ ~X ３each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0107] In formula (2-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (2-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (2-1), m is preferably 2 or 4, and more preferably 2. In formula (2-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that in formula (2-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0108] In the formula (2-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１ The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0109] In formula (2-1), R １２ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R １２ The substituent in R is preferably a monovalent substituent, such as a halogen atom. １２ When R is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. １２ is preferably an unsubstituted phenylene group. １２The phenylene group in is preferably a 1,2-phenylene group.

[0110] In formula (2-1), R ２ and R ３ A preferred embodiment of the structure represented by formula (2-2) included in the formula (2-1) is the same as the preferred embodiment of formula (1-1) above. In formula (2-1), m is 2 or more, and R ２ If two or more are included, ２ In formula (2-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0111] R in formula (2-1) ２ Specific examples of the compound are shown below, but are not limited to these. In the following structures, * represents X in formula (2-1). Ａ represents the bonding site with M in formula (2-1).

[0112] R in formula (2-1) ３ Specific examples of the formula (2-1) are shown below, but the formula is not limited thereto. Ａ represents the bonding site with M in formula (2-1).

[0113] From the viewpoint of the stability of the specific metal complex, one of the preferred embodiments of the present invention is one in which the specific metal complex does not have any monodentate ligand other than cyclopentadienyl.

[0114] The specific metal complex preferably generates an amine when heated to 250°C. The temperature is preferably 230°C, more preferably 200°C, and even more preferably 180°C. In the present invention, a specific metal complex is defined as generating an amine at X°C if a solution of the specific metal complex at the same concentration as the resin composition of the present invention dissolved in the same solvent as the resin composition of the present invention is prepared and heated at X°C, and an amine is generated in an amount of 10 mol% or more relative to the total molar amount of the specific metal complex. Furthermore, from the viewpoint of the breaking elongation of the resulting cured product, the pKa of the conjugate acid of the amine is preferably 3 or more, more preferably 6 or more. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less. Furthermore, from the viewpoint of storage stability, the pKa of the conjugate acid of the specific metal complex itself is preferably less than 3, preferably -5 or less, and more preferably -10 or less. pKa refers to the equilibrium constant Ka of a dissociation reaction in which hydrogen ions are released from an acid, expressed as its negative common logarithm, pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark). When the conjugate acid has multiple pKa values, it is preferable that at least one of them is within the above range.

[0115] The solubility parameter of the specific metal complex is preferably an SP (solubility parameter) value of 9 or more, more preferably 10 or more. There is no particular upper limit to the SP value, and it may be, for example, 30 or less. In this specification, the SP value is determined by the Hoy method (H.L. Hoy, Journal of Painting, 1970, Vol. 42, 76-118), unless otherwise specified. In addition, although the unit of the SP value is omitted, the unit is cal １／２ cm －３／２ is.

[0116] [Molecular Weight] The molecular weight of the specific metal complex is preferably 200 to 2,000, more preferably 250 to 1,500, and even more preferably 300 to 1,000.

[0117] [Synthesis Method] The specific metal complex can be synthesized, for example, by reacting a titanium alkoxide with a compound having an alkoxy group or a carboxyl group. Alternatively, other known synthesis methods may be used for synthesis, and the synthesis method is not particularly limited.

[0118] Specific examples of the specific metal complex include, but are not limited to, A-1 to A-43 used in the examples.

[0119] The content of the specific metal complex relative to the total solid content of the resin composition of the present invention is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.10% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. One type of specific metal complex may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above range.

[0120] The resin composition of the present invention preferably contains a polymerizable compound and a polymerization initiator, and more preferably contains a polymerizable compound and a photopolymerization initiator from the viewpoint of enabling exposure development.

[0121] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0122] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0123] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0124] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0125] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0126] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0127] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0128] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0129] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0130] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0131] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0132] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0133] The radical crosslinking agent is preferably a radical crosslinking agent having at least one structure selected from the group consisting of a urea bond, a urethane bond, and an amide bond (hereinafter also referred to as "crosslinking agent U"). In the present invention, the urea bond refers to a radical crosslinking agent having at least one structure selected from the group consisting of *-NR Ｎ —C(═O)—NRＮ - is a bond represented by *, and R Ｎ each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom, preferably a bonding site with a hydrocarbon group. In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom, preferably a bonding site with a hydrocarbon group. In the present invention, the amide bond is *-C(=O)-NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom, preferably a bonding site with a hydrocarbon group. When a resin composition contains crosslinker U, chemical resistance, resolution, etc. may be improved. The mechanism by which this effect is achieved is unclear; however, it is thought that, for example, during curing by heating, a portion of crosslinker U thermally decomposes, generating amines, etc., which then promote cyclization of the polyimide precursor. Crosslinker U may have only one urea bond, urethane bond, or amide bond, or may have two or more structures selected from the group consisting of urea bonds, urethane bonds, and amide bonds. The total number of urea bonds, urethane bonds, and amide bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0134] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0135] The crosslinking agent U preferably has a structure represented by the following formula (U-1): In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents a single bond, —O—, or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２ represents a single bond or an (n+1)-valent organic group, X represents a radical polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

[0136] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferable. Ｕ１ The bonding site with A in R is preferably a hydrocarbon group. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a bond between these groups. Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0137] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, the structure is a polyalkyleneoxy group), and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, and cyano group may be present at any position in the crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that the crosslinking agent U has at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, and cyano group linked to at least one radically polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond, a urethane bond, or an amide bond (hereinafter also referred to as "linking group L2-1"). In particular, when the crosslinking agent U contains only one radically polymerizable group, it is preferable that the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, and a cyano group are linked via a linking group containing a urea bond, a urethane bond, or an amide bond (hereinafter also referred to as "linking group L2-2").When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Furthermore, preferred embodiments of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U has a hydroxy group.

[0138] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond, a urethane bond, or an amide bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds, urethane bonds, or amide bonds, it is preferable that one of the urea bonds, urethane bonds, or amide bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, as in indole and benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond, a urethane bond, or an amide bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0139] The number of atoms (linking chain length) between the urea bond, urethane bond, or amide bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds, urethane bonds, or amide bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds, urethane bonds, or amide bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond, urethane bond, or amide bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond, urethane bond, or amide bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these linked objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0140] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0141] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0142] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0143] Specific examples of the crosslinking agent U include the following compounds, but the crosslinking agent U is not limited to these.

[0144] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0145] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0146] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0147] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. It is preferably a compound having multiple groups in its molecule that promote a reaction to form a covalent bond with other compounds in the composition or their reaction products upon exposure to light by the photoacid generator or photobase generator described above. A compound having multiple groups in its molecule that promote a reaction to form a covalent bond with other compounds in the composition or their reaction products upon exposure to light by the photoacid generator or photobase generator described above is preferred. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure step. The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group. A compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkyleneurea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used. Oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As for the amino group-containing compounds, crosslinking agents using melamine are referred to as melamine-based crosslinking agents, crosslinking agents using glycoluril, urea, or alkyleneurea are referred to as urea-based crosslinking agents, crosslinking agents using alkyleneurea are referred to as alkyleneurea-based crosslinking agents, and crosslinking agents using benzoguanamine are referred to as benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0148] Examples of compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0149]

[0150] R １００ represents an alkyl group or an acyl group. １０１ and R １０２ each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0151] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0152]

[0153] In the formula, X represents a single bond or a divalent organic group, and each R １０４ each independently represents an alkyl group or an acyl group, R １０３ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ A group represented by R ４ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ５ represents a group that is eliminated by the action of an acid. １０５each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. A group that decomposes under the action of an acid to produce an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ R in the group represented by ５ For example, -C(R ３６ ) (R ３７ ) (R ３８ ), -C(R ３６ ) (R ３７ ) (OR ３９ ), -C(R ０１ ) (R ０２ ) (OR ３９ In the formula, R ３６ ~R ３９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ and R ３７ may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 16 carbon atoms. The aralkyl group refers to an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have a known substituent.

[0154] R ０１ and R ０２ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0155] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc., more preferably a tertiary alkyl ester group or an acetal group.

[0156] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred embodiments of the above compound are the same as the preferred embodiments of the above crosslinking agent U, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

[0157] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compound is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0158]

[0159]

[0160]

[0161] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferred.

[0162] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0163] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0164] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0165] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0166] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , 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, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0167] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0168] - Epoxy Compound (Compound Having Epoxy Group) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition and suppressing warpage.

[0169] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the modulus of elasticity and suppresses warpage. The polyethylene oxide group refers to a group having two or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0170] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark, the same applies hereinafter) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark, the same applies below) BEO-20E, Rikaresin BEO-60E, Rikaresin HBE-100, Rikaresin DME-100, Rikaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Epolead (registered trademark, the same applies hereinafter) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, the same applies hereinafter) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-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 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like.The following compounds are also preferably used:

[0171]

[0172] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0173] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0174] -Oxetane Compound (Compound Having an Oxetanyl Group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more.

[0175] - Benzoxazine Compound (Compound Having a Benzoxazolyl Group) - Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, thermal shrinkage is reduced, thereby suppressing the occurrence of warping.

[0176] Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0177] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0178] [Photopolymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, the photoradical polymerization initiator may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0179] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0180] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A can be mentioned, the contents of which are incorporated herein by reference.

[0181] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0182] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone initiators described in JP-A-10-291969 and the acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference. Furthermore, 2,4,6-trimethylbenzoyldiphenylphosphine oxide can also be suitably used as the acylphosphine oxide. Furthermore, examples of commercially available acylphosphine oxide initiators include Omnirad TPO and Omnirad TPO-S.

[0183] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0184] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0185] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0186] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0187] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0188] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, 5-(4-isopropylphenylthio)-1,2-indandione, and 2-(O-acetyl)oxime. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound serving as a photoradical polymerization initiator has a linking group >C=N--O--C(=O)-- in the molecule.

[0189]

[0190] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Omnirad 1312, Omnirad 1316, and Omnirad 1317 (all manufactured by IGM Resins). B.V.), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831 and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemische Co., Ltd.), SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds having the following structure can also be used.

[0191] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0192] As the photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring can be used. ＯＸ１ It is also possible to use an oxime compound having the aromatic ring group Ar ＯＸ１ Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0193] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). In the formula, RＸ１ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group; R Ｘ２ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R Ｘ３ ~R Ｘ１４ each independently represents a hydrogen atom or a substituent. Ｘ１０ ~R Ｘ１４ At least one of the groups is an electron-withdrawing group.

[0194] In the above formula, R Ｘ１２ is an electron-withdrawing group, and R Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ is preferably a hydrogen atom.

[0195] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0196] Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0197] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0198] The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0199] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0200] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, WO 2016-532675, paragraphs 0407 to 0412, and WO 2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0201] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0202] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0203] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0204] [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 Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0205] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0206] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0207] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. When the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Examples of nonionic base generators include compounds represented by formula (B1) or (B2) described in paragraphs 0275 to 0285 of WO 2021 / 112189, compounds represented by formula (N1) described in paragraphs 0102 to 00162 of WO 2020 / 066416, and preferred base generators include the thermal base generators described in paragraphs 0013 to 0041 of WO 2020 / 054226. The contents of these compounds are incorporated herein by reference.

[0208] Examples of the base generator include, but are not limited to, the following compounds:

[0209]

[0210] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0211] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0212] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0213] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0214] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0215] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0216] 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 alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0217] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0218] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0219] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0220] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0221] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0222] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0223] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0224] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0225] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0226] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0227] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0228] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the formula below, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0229]

[0230] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of suitable silane coupling agents include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. Ｓ１is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R Ｓ２ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0231] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0232] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0233] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0234] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0235] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0236] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0237] Other migration inhibitors, for example, other migration inhibitors, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compounds described in paragraph 0166 of WO 2015 / 199219, and the like can be used, the contents of which are incorporated herein by reference.

[0238] Specific examples of the migration inhibitor include the following compounds.

[0239]

[0240] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0241] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0242] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0243] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, tris(2,6-dimethyl-3-hydroxy-4-tert-butyl-benzyl)isocyanurate, and the like, the contents of which are incorporated herein by reference.

[0244] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0245] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0246] <Other Additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101 to 0104, 0107 to 0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0247] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0248] By adding a surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with small thickness unevenness.

[0249] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0250] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0251] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0252] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0253] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0254] [Higher Fatty Acid Derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0255] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0256] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0257] [Thermal Polymerization Initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0258] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0259] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0260] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0261] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by dynamic light scattering using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0262] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0263] The ultraviolet absorbers may be used singly or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber 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, based on the total solid mass of the resin composition.

[0264] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0265] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0266] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0267] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0268] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0269] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0270] [Anti-aggregating Agent] Examples of the anti-aggregating agent include sodium polyacrylate.

[0271] The anti-aggregating agent may be used singly or in combination of two or more. When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total mass of the solid content of the resin composition.

[0272] [Phenol-based compounds] Examples of phenol-based 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, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0273] The phenolic compound may be used alone or in combination of two or more. When the resin composition contains a phenolic compound, the content of the phenolic compound 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, based on the total solid mass of the resin composition.

[0274] [Other Polymer Compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified compounds into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0275] The other polymer compounds may be used singly or in combination of two or more. When the resin composition contains the other polymer compounds, the content of the other polymer compounds 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, based on the total solid mass of the resin composition.

[0276] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0277] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0278] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0279] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0280] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0281] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0282] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product according to the first aspect of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0283] The cured product according to the second aspect of the present invention satisfies all of the following conditions (i) to (iv). The cured product according to the first aspect of the present invention preferably satisfies all of the following conditions (i) to (iv). Condition (i): The Young's modulus of the cured product is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the cured product in the temperature range of 25 to 125°C is less than 50 ppm / °C. Condition (iii): The glass transition temperature of the cured product is 240°C or more. Condition (iv): The elongation at break of the cured product is 40% or more. Here, preferred aspects and measurement methods of Young's modulus, thermal expansion coefficient, glass transition temperature, and elongation at break in the above conditions (i) to (iv) are the same as preferred aspects and measurement methods of Young's modulus, thermal expansion coefficient, glass transition temperature, and elongation at break in the above conditions (i) to (iv) for the resin composition of the present invention. In addition, the cured product of the present invention preferably satisfies all of the following conditions (v) to (viii). Condition (v): The Young's modulus of the cured product is 4.5 GPa or more. Condition (vi): The thermal expansion coefficient of the cured product in the temperature range of 25°C to 125°C is less than 40 ppm / °C. Condition (vii): The glass transition temperature of the cured product is 260°C or more. Condition (viii): The breaking elongation of the cured product is 50% or more.

[0284] Hereinafter, the cured product according to the first aspect of the present invention and the cured product according to the second aspect of the present invention will be collectively referred to simply as "the cured product of the present invention" or "cured product".

[0285] <Properties of Cured Product of Resin Composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.

[0286] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0287] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0288] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0289] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0290] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0291] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0292] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a coating film formed by applying the coating composition to a temporary support using the above-described application method can be transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A process for removing excess film from the edge of the substrate may also be performed. Examples of such a process include edge bead rinsing (EBR) and back rinsing. A pre-wetting process may also be employed in which the substrate is coated with various solvents before the resin composition is applied to the substrate to improve the wettability of the substrate.

[0293] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming 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 even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0294] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0295] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0296] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0297] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0298] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0299] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0300] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0301] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0302] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0303] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0304] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0305] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult to remain in the cured film (the obtained cured product), and from the viewpoint of promoting cyclization, it is preferred that the amount remaining before heating is unlikely to decrease due to vaporization, etc. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably 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., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0306] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples of the alkyl ester include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0307] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0308] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0309] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0310] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0311] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0312] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0313] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0314] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0315] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0316] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0317] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0318] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0319] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0320] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. The method of supplying the rinse liquid in the rinse step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, or a combination of these steps.

[0321] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0322] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0323] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent, the basic compound, and the base generator are the same as the preferred aspects of the organic solvent, the basic compound, and the base generator used in the rinse liquid described above. The treatment liquid can be supplied to the pattern using the same method as the rinse liquid described above, and preferred aspects are also the same.

[0324] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. There is no particular limitation on the lower limit of the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When there are two or more types of at least one of the basic compound and the base generator, it is preferable that the total amount thereof is within the above-mentioned range.

[0325] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step, is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0326] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0327] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0328] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0329] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0330] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0331] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0332] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0333] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0334] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0335] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0336] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0337] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0338] <Applications> Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0339] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0340] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0341] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0342] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0343] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0344] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. The details of the surface activation treatment will be described later.

[0345] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0346] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0347] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein by reference.

[0348] (Semiconductor device and manufacturing method thereof) A semiconductor device according to a first aspect of the present invention is a semiconductor device comprising the cured product of the present invention or the laminate of the present invention. The present invention also discloses a manufacturing method of a semiconductor device comprising the manufacturing method of the cured product of the present invention or the manufacturing method of the laminate. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0349] A semiconductor device according to a second aspect of the present invention is a semiconductor device comprising a semiconductor chip, a redistribution layer, and an interlayer insulating film for a redistribution layer that satisfies all of the following conditions (i) to (iv): Condition (i): The Young's modulus of the interlayer insulating film for a redistribution layer is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the interlayer insulating film for a redistribution layer in the temperature range of 25 to 125°C is less than 50 ppm / °C. Condition (iii): The glass transition temperature of the interlayer insulating film for a redistribution layer is 240°C or more. Condition (iv): The fracture elongation of the interlayer insulating film for a redistribution layer is 40% or more.

[0350] Here, the preferred aspects and measurement methods of the Young's modulus, thermal expansion coefficient, glass transition temperature, and breaking elongation in the interlayer insulating film for a rewiring layer under the above conditions (i) to (iv) are the same as the preferred aspects and measurement methods of the Young's modulus, thermal expansion coefficient, glass transition temperature, and breaking elongation under the above conditions (i) to (iv) in the resin composition of the present invention. In addition, it is preferable that the interlayer insulating film for a rewiring layer satisfies all of the following conditions (v) to (viii): Condition (v): The Young's modulus of the interlayer insulating film for a redistribution layer is 4.5 GPa or more. Condition (vi): The thermal expansion coefficient of the interlayer insulating film for a redistribution layer in the temperature range of 25°C to 125°C is less than 40 ppm / °C. Condition (vii): The glass transition temperature of the interlayer insulating film for a redistribution layer is 260°C or more. Condition (viii): The breaking elongation of the interlayer insulating film for a redistribution layer is 50% or more. The interlayer insulating film for a redistribution layer is preferably a layer formed from the resin composition of the present invention. Furthermore, the interlayer insulating film for a redistribution layer is preferably a cured product of the present invention.

[0351] The semiconductor chip in the semiconductor device according to the second aspect is not particularly limited and may be a known semiconductor chip, such as a chip made of a semiconductor such as silicon. The redistribution layer is a layer including wiring and the interlayer insulating film for the redistribution layer. The wiring is not particularly limited and may be a known wiring, such as a metal wiring such as copper wiring. The redistribution layer may be a single layer or a laminate consisting of multiple layers. When the redistribution layer is a laminate, the layers included in the laminate may be made of the same material or different materials. The wiring is preferably electrically connected to the semiconductor chip and in contact with the interlayer insulating film for the redistribution layer. The wiring is preferably electrically insulated by the interlayer insulating film for the redistribution layer.

[0352] The semiconductor device according to the second aspect of the present invention further includes an encapsulant that covers the semiconductor chip, and the redistribution layer preferably has a larger area in a planar view than the semiconductor chip. The encapsulant preferably directly contacts the semiconductor chip and the redistribution layer. The composition of the encapsulant is not particularly limited, but it preferably contains a resin, and epoxy resin or the like is preferred from the viewpoints of heat resistance and adhesion. The encapsulant may be a single layer or a laminate consisting of multiple layers. When the encapsulant is a laminate, the layers included in the laminate may be made of the same material or different materials.

[0353] FIG. 1 shows an example of a semiconductor device according to a second aspect of the present invention. FIG. 1 illustrates a semiconductor device 1 including a semiconductor chip 2, an encapsulant 3 covering the semiconductor chip 2, and a redistribution layer 4 in close contact with the semiconductor chip 2 and the encapsulant 3. The redistribution layer 4 includes wiring 5 and a redistribution layer interlayer insulating film 6. As shown in FIG. 1, the encapsulant 3 covers the surface of the semiconductor chip 2 and is formed over an area larger than the semiconductor chip 2 in a plan view (as viewed from the arrow A). In the redistribution layer 4, the spaces between the wiring 5 are filled with the redistribution layer interlayer insulating film 6. One end of the wiring 5 is connected to a terminal 2a, and the other end is connected to an external connection terminal 7. The entire wiring 5 between the terminal 2a and the external connection terminal 7 is covered with the redistribution layer interlayer insulating film 6. In the semiconductor device according to the second aspect of the present invention, the redistribution layer interlayer insulating film 6 satisfies all of the above-described conditions (i) to (iv). Therefore, it is believed that cracks are unlikely to occur between the redistribution layer interlayer insulating film 6 and the wiring 5 even after a severe TCT test. The semiconductor device shown in FIG. 1 is merely an example, and it goes without saying that the semiconductor device according to the second aspect of the present invention is not limited to this.

[0354] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0355] Synthesis of Polyimide Precursor Synthesis Example A-1 Synthesis of Polyimide Precursor (A-1) 10.4 g (47.6 mmol) of pyromellitic anhydride, 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of pyromellitic anhydride and 4,4'-(4,4''-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. The mixture was then cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 21.1 g (66.0 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 liters of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-1). The polyimide precursor (A-1) is a resin having two repeating units represented by the following formula (A-1). The structure of the repeating units is １ The weight average molecular weight (Mw) of the resin was determined from H-NMR spectrum. The weight average molecular weight (Mw) of the resin was 50,000. Furthermore, synthesis was carried out in the same manner as above, except that the amount of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was changed to 19.6 g (61.2 mmol). The Mw of the resin was 35,000. In the resin compositions described below, the molecular weight of A-1 used is indicated in the "Mw" column of the table.

[0356] [Synthesis Examples A-2 to A-6: Synthesis of Polyimide Precursors (A-2) to (A-6)] Polyimide precursors (A-2) to (A-6) were synthesized in the same manner as for polyimide precursor (A-1), except that the carboxylic acid dianhydride and diamine used were appropriately changed. Polyimide precursors (A-2) to (A-6) are resins having repeating units represented by the following formulas (A-2) to (A-6), respectively. The structures of the repeating units are １ The composition ratios (molar ratios of repeating units) of Resins A-1 to A-6 are shown in the table below. For example, "A / B=8 / 2" means that the repeating unit designated "A" and the repeating unit designated "B" are contained in a molar ratio of 8:2.

[0357]

[0358] Synthesis Example A-7 Synthesis of Polyimide Precursor A-7 5.94 g (27.2 mmol) of pyromellitic anhydride, 5.24 g (27.2 mmol) of trimellitic anhydride, 7.08 g (13.6 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of pyromellitic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), and 2-hydroxyethyl methacrylate. The mixture was then cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 21.1 g (66.0 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (A-7). The polyimide precursor (A-7) is a resin having three repeating units represented by the following formula (A-7). The structure of the repeating units is １ Determined from H-NMR spectrum.

[0359] <Synthesis Examples A-8 to A-9: Synthesis of Polyimide Precursors (A-8) to (A-9)> Polyimide precursors (A-8) to (A-9) were synthesized in the same manner as for polyimide precursor (A-7), except that the carboxylic acid dianhydride and diamine used were appropriately changed. Polyimide precursors (A-8) to (A-9) are resins having repeating units represented by the following formulas (A-8) to (A-9), respectively. The repeating unit structures are １ The composition ratios (molar ratios) of the polyimide precursors (A-7) to (A-9) are shown in the table below.

[0360]

[0361] Synthesis Example A-10: Synthesis of Polyimide (A-10) In a flask equipped with a condenser and a stirrer, 10.4 g (47.6 mmol) of pyromellitic anhydride and 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) were dissolved in 125.0 g of N-methylpyrrolidone (NMP) while removing water. Next, 21.1 g (66.0 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was added, and the mixture was stirred at 25°C for 3 hours and then at 45°C for an additional 3 hours. Next, 21.5 g (200 mmol) of pyridine, 17.4 g (170 mmol) of acetic anhydride, and 100 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours, and then 50 g of N-methylpyrrolidone (NMP) was added to dilute the mixture. This reaction solution was precipitated in 1.5 liters of methanol and stirred at 3000 rpm for 15 minutes. The resin was removed by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried under reduced pressure at 40°C for 1 day to obtain polyimide A-10. Polyimide (A-10) is a resin having a repeating unit represented by the following formula (A-10). The structure of the repeating unit is １ The content ratio (molar ratio) of each repeating unit was A / B=7 / 3.

[0362] Synthesis Example P-1: Synthesis of Polyimide Precursor (P-1) 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, 6,000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6,000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was again filtered and dried at 45°C under reduced pressure for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. Then, 3,000 g of ethanol was added, and the precipitate was collected by filtration. The resulting precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (AmberTec) were added thereto and stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of polyimide precursor (P-1). The structure of polyimide precursor (P-1) is represented by the following formula (P-1). The structure of the repeating unit is １ Determined from H-NMR spectrum.

[0363] Synthesis Examples P-2 and P-4: Synthesis of Polyimide Precursors (P-2) and (P-4) Polyimide precursors (P-2) and (P-4) were synthesized in the same manner as for polyimide precursor (P-1), except that the carboxylic acid dianhydride and diamine used were changed appropriately. In the synthesis of P-3, the following compound (AN-1) was used as the carboxylic acid dianhydride. Polyimide precursors (P-2) and (P-4) are resins having repeating units represented by the following formulas (P-2) and (P-4), respectively. The structures of the repeating units are １ Determined from H-NMR spectrum.

[0364] Synthesis Example AN-1: Synthesis of Anhydride AN-1 In a flask equipped with a condenser, 51.8 g (246 mmol) of trimellitic anhydride chloride was dissolved in 150 mL of tetrahydrofuran and cooled to -10°C. Subsequently, 19.9 g (252 mmol) of pyridine and 0.73 g (6 mmol) of 4-dimethylaminopyridine were added. Subsequently, a solution of 13.1 g (120 mmol) of 4-aminophenol dissolved in 150 mL of tetrahydrofuran was added dropwise using a dropping funnel over 2 hours, followed by stirring at a temperature ranging from -10°C to 0°C for 1 hour. The reaction solution was heated to 20°C to 25°C, stirred for an additional 3 hours, and then diluted with 200 mL of acetonitrile. Subsequently, the reaction solution was crystallized in 3 L of 1 N (mol / L) aqueous hydrochloric acid solution, filtered, washed with dilute hydrochloric acid and water, and then the crystals were removed and reslurried in 500 mL of ethyl acetate. After filtering, the mixture was transferred to a flask, 200 mL of acetic anhydride was added, and the mixture was stirred at 80°C for 3 hours. The mixture was filtered, washed with ethyl acetate, and then vacuum dried at 60°C to obtain 35 g of anhydride AN-1. １ This was confirmed by H-NMR spectrum.

[0365] Synthesis Example P-3: Synthesis of Polyimide Precursor (P-3) 20.5 g (43.6 mmol) of the anhydride (AN-1) synthesized above, 11.5 g (88 mmol) of 2-hydroxyethyl methacrylate, 0.03 g of hydroquinone, 15.3 g (193 mmol) of pyridine, and 90 g of diglyme were mixed and stirred at 60° C. for 5 hours to produce a diester of anhydride (AN-1) and 2-hydroxyethyl methacrylate. The mixture was then cooled to −20° C., and 10.6 g (88 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was then stirred for 2 hours, yielding a white precipitate of pyridinium hydrochloride. Next, 12.9 g (40 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 90 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. Next, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 4 liters of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (P-3). Polyimide precursor (P-3) is a resin having a repeating unit represented by the following formula (P-3). The structure of the repeating unit is １ Determined from H-NMR spectrum.

[0366] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In each comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "Amount Added" column in each column of the table. The obtained resin composition and comparative composition were pressure-filtered using a UPE (ultra-high molecular weight polyethylene) filter with a pore width of 0.2 μm. In the table, "-" indicates that the composition did not contain the corresponding component.

[0367]

[0368]

[0369]

[0370]

[0371] Details of each component listed in the table are as follows:

[0372] [Resins (Polyimide Precursors or Polyimides)] A-1 to A-10: Polyimide precursors (A-1) to (A-9) and polyimide (A-10) synthesized above. P-1 to P-4: Polyimide precursors (P-1) to (P-4) synthesized above.

[0373] [Polymerizable compounds] B-1: SR-209 (manufactured by Sartomer Corporation) B-2: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-3 to B-6: Compounds having the following structures

[0374] [Solvent] C-1: γ-butyrolactone C-2: dimethyl sulfoxide C-3: ethyl lactate C-4: NMP

[0375] [Polymerization initiators] D-1: IRGACURE OXE 01 (manufactured by BASF) D-2: IRGACURE OXE 02 (manufactured by BASF) D-3: Omnirad 1316 (manufactured by IGM Resins B.V.) D-4: Omnirad 1312 (manufactured by IGM Resins B.V.) D-5: Omnirad TPO-S (manufactured by IGM Resins B.V.) D-6: TR-PBG-305 (manufactured by Tronly) D-7: TR-PBG-3057 (manufactured by Tronly) D-8 to D-9: Compounds having the following structure The structures of the polymerization initiators are as follows:

[0376] [Sensitizer] J-1: N-phenyldiethanolamine

[0377] [Rust inhibitor (migration inhibitor)] E-1: Compound having the following structure

[0378] [Adhesion agents (metal adhesion improvers)] F-1: Compounds having the following structures F-2: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) F-3: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) F-4 to F-5: Compounds having the following structures

[0379] [Polymerization inhibitor] G-1: 1,4-benzoquinone G-2: 4-methoxyphenol G-3: 1,4-dihydroxybenzene G-4: Compound having the following structure

[0380] [Base Generator] H-1 to H-2: Compounds having the following structures

[0381] [Metal Complexes] I-1 to I-4: Compounds having the following structures

[0382] <Measurement and Evaluation> [Measurement of Elongation (Elongation at Break)] In each of the Examples and Comparative Examples, a resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes, to obtain a resin composition layer having a uniform thickness of about 15 µm after film formation on the silicon wafer. The obtained resin composition layer was exposed to a Ushio exposure machine (light source: 500 W / m ２ Ultra-high pressure mercury lamp) at 400 mJ / cm ２The resin composition layer (resin layer) was exposed to light at an exposure energy of 100 keV using a dumbbell-shaped mask. The dumbbell shape was a dumbbell No. 7 shape as described in JIS K 6251:2017. The exposed resin composition layer (resin layer) was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to remove unexposed areas. The temperature was then increased at a rate of 10°C / min under a nitrogen atmosphere, and the layer was heated to 230°C for 3 hours. The cured resin layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width: 2 mm, sample length: 35 mm). The obtained test specimens were subjected to measurement of longitudinal elongation in accordance with JIS-K7161-1 (2014) using a tensile tester (Instron Model 5965) at a crosshead speed of 5 mm / min under an environment of 25°C and 65% RH (relative humidity). Each evaluation was performed six times, and the arithmetic mean value of the elongation at which the test specimen broke was used as the index value. Evaluation was performed using the above index value according to the following evaluation criteria, and the evaluation results are recorded in the "Elongation" column in the table. -Evaluation Criteria- A: The index value was 50% or more. B: The index value was 40% or more but less than 50%. C: The index value was less than 40%.

[0383] [Measurement of Young's Modulus] The Young's modulus of the test piece prepared in the above elongation measurement was measured in accordance with JIS-K7161-1 (2014) using a DMA850 (TA Instruments) at a crosshead speed of 5 mm / min, 25°C, and 65% RH (relative humidity). The obtained Young's modulus was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "Young's Modulus" column in the table. -Evaluation Criteria- A: Young's modulus was 4.5 GPa or more. B: Young's modulus was 3.5 GPa or more and less than 4.5 GPa. C: Young's modulus was less than 3.5 GPa.

[0384] [Measurement of CTE] The CTE of the test specimens prepared above at 25°C to 125°C was measured using a TMA450 (TA Instruments). The heating and cooling conditions during evaluation were, for example, as follows (1) to (4): (1) Heating from room temperature to 130°C at a heating rate of 5°C / min. (2) Cooling from 130°C to 10°C at a heating rate of 5°C / min. (3) Heating from 10°C to 220°C at a heating rate of 5°C / min. (4) Natural cooling to room temperature. The elongation (displacement) of the sample was measured during the heating and cooling processes of (1) to (4) above, and the elongation (displacement) of the sample at 25°C and 125°C during process (3) was divided by the temperature to calculate the thermal expansion coefficient. (For example, if the length of the sample at 25°C was 50 mm and the length of the sample at 125°C was 50.2 mm, the displacement was calculated to be 0.4% = 4000 ppm, and the thermal expansion coefficient was 4000 / (125-25) = 40 ppm / °C.) The obtained CTE was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "CTE" column in the table. -Evaluation criteria- A: CTE was less than 40 ppm / °C. B: CTE was 40 ppm / °C or more and less than 50 ppm / °C. C: CTE was 50 ppm / °C or more.

[0385] [Measurement of Tg] The Tg of the test piece prepared above was measured using a DMA850 (TA Instruments). Specifically, the temperature conditions of the cured product were changed in the following order (1) to (2) to measure the glass transition temperature. (1) The temperature was increased from 25°C to 350°C at a rate of 5°C / min. (2) The temperature was cooled from 350°C to 25°C. The obtained Tg was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "Tg" column in the table. -Evaluation criteria- A: Tg was 260°C or higher. B: Tg was 240°C or higher but less than 260°C. C: Tg was less than 240°C.

[0386] In the measurements of elongation, Young's modulus, CTE, and Tg, the above-mentioned exposure and development were omitted, and the measurements were carried out using test pieces obtained by punching the above-mentioned dumbbell-shaped test pieces from the cured product after peeling using a punching tool. All evaluation results were similar in all Examples and Comparative Examples.

[0387] [Evaluation of TCT crack resistance] In each example and comparative example, a resin composition or a comparative composition was applied by spin coating to a silicon wafer on which 10 μm L / S (line and space) Cu wiring had been formed, to form a resin composition layer. The silicon wafer to which the obtained resin composition layer had been applied was dried on a hot plate at 100° C. for 5 minutes, to obtain a uniform resin composition layer having a thickness of about 15 μm after film formation on the silicon wafer. The obtained resin composition layer was exposed to a Ushio exposure machine (light source: 500 W / m ２ Ultra-high pressure mercury lamp) at 400 mJ / cm ２ The entire surface of the silicon wafer was exposed with an exposure energy of 1000 s. The exposed resin composition layer was heated at a rate of 10°C / min in a nitrogen atmosphere and heated at 230°C for 3 hours to obtain a cured product. The obtained cured product was subjected to a TCT test (ES-57L manufactured by Hitachi Global Life Solutions, Inc., 1000 cycles of -55°C and 200°C), and the presence or absence of cracks at the interface between the Cu wiring and the cured product was observed using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation). (Evaluation criteria) A: 0 cracks were observed out of 10 observation points. B: 1 crack was observed out of 10 observation points. C: 2 to 3 cracks were observed out of 10 observation points. D: Cracks were observed in all 10 observation points.

[0388] <Examples 101 to 159> In Examples 1 to 59, in place of the Ushio exposure device, a stepper (FPA-3000 i5 (manufactured by Canon Corporation)) or a direct exposure device (Adtec DE-6UH III) was used as the light source when exposing the resin composition layer to light in the evaluation of TCT crack resistance, and the TCT crack resistance was evaluated without changing the other test methods. In all of the Examples, the same results as in Examples 1 to 84 were obtained, respectively.

[0389] [Evaluation of Resolution] The resin composition used in each example was applied in the form of a layer by spin coating to the surface of a thin copper layer formed on a resin substrate on which a thin copper layer had been formed, and dried at 100°C for 5 minutes to form a resin composition layer with a film thickness of 7 μm. The resulting film was then exposed to light using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)). The exposure was carried out at a wavelength of 365 nm through a 7 μm hole pattern mask. The film was then developed with cyclopentanone for 2 minutes, rinsed with PGMEA for 30 seconds, and heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at 230°C for 3 hours to obtain a 7 μm hole pattern. The resin composition of the present invention has excellent resolution and can be used as a high-definition interlayer insulating film. Similar results were obtained when γ-butyrolactone was used instead of cyclopentanone.

[0390] From the above results, it can be seen that the films formed from the resin compositions of the present invention have excellent TCT crack resistance. The comparative compositions of Comparative Examples 1 to 4 do not meet the specifications for the resin compositions of the present invention in terms of one of Young's modulus, CTE, Tg, and elongation. It can be seen that these comparative compositions have poor adhesion after the TCT.

[0391] [Evaluation of Resolution] The resin composition used in each example was applied in the form of a layer by spin coating to the surface of a thin copper layer formed on a resin substrate on which a thin copper layer had been formed, and dried at 100°C for 5 minutes to form a resin composition layer with a film thickness of 7 μm. The resulting film was then exposed to light using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)). The exposure was carried out at a wavelength of 365 nm through a 7 μm hole pattern mask. The film was then developed with cyclopentanone for 2 minutes, rinsed with PGMEA for 30 seconds, and heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at 230°C for 3 hours to obtain a 7 μm hole pattern. The resin composition of the present invention has excellent resolution and can be used as a high-definition interlayer insulating film. Similar results were obtained when γ-butyrolactone was used instead of cyclopentanone.

[0392] REFERENCE SIGNS LIST 1 semiconductor device 2 semiconductor chip 2a terminal 3 sealing material 4 rewiring layer 5 wiring 6 interlayer insulating film 7 external connection terminal

Claims

1. A resin composition containing a polyimide or a polyimide precursor, The resin composition was heated at 230° C. for 3 hours to obtain a film-like cured product having a thickness of 15 μm, which satisfies all of the following conditions (i) to (iv): Resin composition. Condition (i): The Young's modulus of the cured product is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the cured product in the temperature range of 25° C. to 125° C. is less than 50 ppm / ° C. Condition (iii): the glass transition temperature of the cured product is 240° C. or higher Condition (iv): The breaking elongation of the cured product is 40% or more.

2. The resin composition according to claim 1, wherein the cured product satisfies all of the following conditions (v) to (viii): Condition (v): the Young's modulus of the cured product is 4.5 GPa or more. Condition (vi): The thermal expansion coefficient of the cured product in the temperature range of 25° C. to 125° C. is less than 40 ppm / ° C. Condition (vii): The glass transition temperature of the cured product is 260° C. or higher. Condition (viii): The breaking elongation of the cured product is 50% or more.

3. The resin composition according to claim 1 or 2, further comprising a metal complex having a π-conjugated site containing a nitrogen atom.

4. The resin composition according to claim 1 or 2, wherein the polyimide precursor contains a repeating unit represented by the following formula (1): 【Chemistry 1】 In formula (1), Z 1 is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, Y 1 is a divalent organic group, A 1 and A 2 each independently represents an oxygen atom or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; R 1 and R 2 At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond.

5. A polyimide precursor including a repeating unit represented by the following formula (1): A metal complex having a π-conjugated site containing a nitrogen atom, Resin composition. 【Chemistry 2】 In formula (1), Z 1 is a tetravalent organic group containing two or more ether groups and an aromatic ring structure, Y 1 is a divalent organic group, A 1 and A 2 each independently represents an oxygen atom or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; R 1 and R 2 At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond.

6. Z in the formula (1) 1 The resin composition according to claim 4 , wherein is a group represented by the following formula (a) or formula (b): 【Chemistry 3】 In formula (a), R a1 each independently represents a monovalent group, m1 represents an integer of 0 to 3, R a2 each independently represents a monovalent group, m2 represents an integer of 0 to 4, R a3 each independently represents a monovalent group, m3 represents an integer of 0 to 3, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1). In formula (b), R b1 each independently represents a monovalent group, n1 represents an integer of 0 to 3, R b2 each independently represents a monovalent group, n2 represents an integer of 0 to 4, R b3 each independently represents a monovalent group, n3 represents an integer of 0 to 4, R b4 each independently represents a monovalent group; n4 represents an integer of 0 to 3; J 1 and J. 2 each independently represents a hydrogen atom, an alkyl group or a trifluoromethyl group, and *1 to *4 each represent a bonding site with the carbonyl group in formula (1).

7. Y in the formula (1) 1 The resin composition according to claim 4, wherein is a divalent organic group represented by the following formula (Y-1): 【Chemistry 4】 In formula (Y-1), R 4 ~R 11 are each independently a hydrogen atom or a monovalent group; R 4 ~R 11 At least one of R is an alkyl group, a fluorine atom, a trifluoromethyl group, or an alkoxy group. 6 and R 8 , R 7 and R 9 may be bonded to form a ring structure, and each * represents a bonding site with the nitrogen atom in formula (1).

8. The resin composition according to claim 3, wherein the metal complex includes a partial structure represented by the following formula (1-1) as a structure including a π-conjugated portion including a nitrogen atom: 【Chemistry 5】 In formula (1-1), X 1 ~X 3 each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

9. The resin composition according to claim 1 , 2 or 5 , wherein the polyimide precursor has a weight average molecular weight of 40,000 or more.

10. The resin composition according to claim 1 , further comprising a polymerizable compound and a photopolymerization initiator.

11. The resin composition according to claim 1 , which is used for forming an interlayer insulating film for a rewiring layer.

12. A cured product obtained by curing the resin composition according to claim 1 , 2 or 5 .

13. A laminate comprising two or more layers made of the cured product according to claim 12, and a metal layer between any two of the layers made of the cured product.

14. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to claim 1, 2 or 5 onto a substrate to form a film.

15. The method for producing a cured product according to claim 14, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.

16. The method for producing a cured product according to claim 14, further comprising a heating step of heating the film at 50 to 450°C.

17. A method for producing a laminate, comprising the method for producing a cured product according to claim 14.

18. A method for producing a semiconductor device, comprising the method for producing a cured product according to claim 14.

19. A semiconductor device comprising the cured product according to claim 12.

20. All of the following conditions (i) to (iv) are satisfied: cured product. Condition (i): The Young's modulus of the cured product is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the cured product in the temperature range of 25 to 125° C. is less than 50 ppm / ° C. Condition (iii): the glass transition temperature of the cured product is 240° C. or higher Condition (iv): The breaking elongation of the cured product is 40% or more.

21. A semiconductor chip; A redistribution layer; The redistribution layer includes a wiring and an interlayer insulating film for the redistribution layer that satisfies all of the following conditions (i) to (iv): Semiconductor device. Condition (i): the Young's modulus of the interlayer insulating film for redistribution layer is 3.5 GPa or more. Condition (ii): The thermal expansion coefficient of the interlayer insulating film for a redistribution layer in the temperature range of 25 to 125° C. is less than 50 ppm / ° C. Condition (iii): the glass transition temperature of the interlayer insulating film for a redistribution layer is 240° C. or higher. Condition (iv): The interlayer insulating film for a redistribution layer has a breaking elongation of 40% or more.

22. Further comprising an encapsulant for covering the semiconductor chip; The rewiring layer has an area larger than that of the semiconductor chip in a plan view.

22. The semiconductor device of claim 21.

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