Method for manufacturing a container and method for storing a resin composition

Abstract

To provide a manufacturing method of a container excellent in temporal stability of a resin composition, and a storage method of the resin composition excellent in temporal stability of the resin composition.SOLUTION: A manufacturing method of a container comprises a step of filling a resin composition containing at least one polymerization initiator selected from the group consisting of an a ring formation resin or a resin of its precursor, as well as, an oxime polymerization initiator and a metallocene polymerization initiator in a storage container to form a container, and a step of storing the container under a temperature condition of less than 0°C, wherein both the i-line transmittance and the h-line transmittance of the storage container are 1% or less, and a storage method of the resin composition.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a container and a method for storing a resin composition.

Background Art

[0002] Cyclized resins such as polyimide are excellent in heat resistance, insulation, etc., and are thus applied to various uses. Although not particularly limited, examples of the above uses include materials for insulating films and encapsulants, or utilization as protective films when taking a semiconductor device for mounting as an example. Further, it is also used as a base film or coverlay of a flexible substrate.

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

[0004] For example, Patent Document 1 describes a method of filling a container with a binder composition for a storage device electrode containing at least one polymer selected from the group consisting of (A) a polyamic acid, a polyamic acid derivative, and an imidized polymer thereof and water, and storing it, wherein the ratio of the volume of the void part excluding the volume occupied by the binder composition for the storage device electrode to the internal volume of the container is 1 to 20%, and it is stored at a temperature of 0°C or higher and 40°C or lower. A method for storing a binder composition for a storage device electrode is described.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a method for producing a container excellent in the temporal stability of a resin composition and a method for storing a resin composition excellent in the temporal stability of the resin composition.

Means for Solving the Problems

[0007] Examples of typical embodiments of the present invention are shown below. <1> A step of filling a storage container with a resin composition containing a resin which is a cyclic resin or a precursor thereof, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator to obtain a container, and a step of storing the container under a temperature condition of less than 0°C, wherein the i-line transmittance and the h-line transmittance of the storage container are both 1% or less A method for producing a container. <2> The method for producing a container according to <1>, wherein the polymerization initiator contains at least one of the compounds represented by any of the following formulas (D-1) to (D-11). [Chemistry] <3> The method for manufacturing the container according to <1> or <2>, wherein the porosity of the container represented by the following formula is 0.01 to 30% by volume. Porosity (%) = (1 - (volume of the resin composition in the container / capacity of the storage container)) x 100 <4> The method for manufacturing the container according to any one of <1> to <3>, wherein the porosity is 0.1 to 20% by volume. <5> The method for manufacturing the container according to any one of <1> to <4>, wherein the porosity is 1 to 15% by volume. <6> The method for manufacturing the container according to any one of <1> to <5>, wherein the porosity is 5 to 15% by volume. <7> The method for manufacturing the container according to any one of <1> to <6>, wherein both the i-line transmittance and the h-line transmittance of the storage container are 0.1% or less. <8> The method for manufacturing the container according to any one of <1> to <7>, wherein both the i-line transmittance and the h-line transmittance of the storage container are 0.01% or less. <9> The method for manufacturing the container according to any one of <1> to <8>, wherein the wall of the storage container has two or more resin layers. <10> The method for manufacturing the container according to any one of <1> to <9>, wherein the resin composition contains at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and ethyl lactate as a solvent. <11> The method for manufacturing the container according to any one of <1> to <10>, wherein the viscosity of the resin composition at 25°C is 50 to 5000 cp. <12> The method for manufacturing the container according to any one of <1> to <11>, wherein the water content in the total mass of the resin composition is 1.0% by mass or less. <13> The method for manufacturing the container according to any one of <1> to <12>, wherein the resin composition contains a component having a polymerizable group. <14> The method for manufacturing the container according to any one of <1> to <13>, wherein the resin composition contains a sensitizer. <15> A storage method for storing in a storage container a resin composition containing a resin that is a cyclized resin or a precursor thereof, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator, wherein both the i-line transmittance and the h-line transmittance of the storage container are 1% or less, the storage is performed under a temperature condition of less than 0°C A method for storing a resin composition. <16> The method for storing a resin composition according to <15>, wherein the polymerization initiator contains at least one of the compounds represented by any of the following formulas (D-1) to (D-11). [Chemical formula] <17> The method for storing a resin composition according to <15> or <16>, wherein the porosity of the resin composition in the storage container during storage is 0.01 to 30% by volume as represented by the following formula. Porosity (%) = (1 - (volume of the resin composition in the storage container / capacity of the storage container)) x 100 [Advantages of the Invention]

[0008] According to the present invention, there are provided a method for manufacturing a container excellent in the stability over time of a resin composition, and a method for storing a resin composition excellent in the stability over time of the resin composition. [Brief Description of the Drawings]

[0009]

Figure 1

Figure 2

Figure 3

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments. In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively. In this specification, the term "step" means not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended action of that step can be achieved. In the notation of a group (atomic group) in this specification, a notation that does not indicate substitution or non-substitution includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent together with the group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of the light used for exposure include actinic rays or radiation such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", or either one, "(meth)acrylic" means both "acrylic" and "methacrylic", or either one, and "(meth)acryloyl" means both "acryloyl" and "methacryloyl", or either one. In this specification, Me in a structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the components of the composition. Also, in this specification, the solid content concentration is the mass percentage of the components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation), and connecting in series a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all of the above are manufactured by Tosoh Corporation) as columns. Unless otherwise specified, those molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, such as in the case of low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Further, unless otherwise specified, detection in GPC measurement is carried out using a detector with a UV (ultraviolet) wavelength of 254 nm. In this specification, regarding the positional relationship of each layer constituting the laminate, when described as "upper" or "lower", there may be another layer above or below the reference layer among the plurality of layers being focused on. That is, a third layer or element may be interposed between the reference layer and the above-mentioned other layer, and the reference layer and the above-mentioned other layer do not necessarily have to be in contact. Further, unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "upper", or, when there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such setting of the up and down directions is for convenience in this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to the component as each component contained in the composition. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23 °C, the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50%RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Method for manufacturing a container) The method for manufacturing a container of the present invention includes a step of filling a storage container with a resin composition containing a cyclic resin or a resin which is a precursor thereof (hereinafter also referred to as "specific resin"), an oxime-based polymerization initiator, and at least one polymerization initiator selected from the group consisting of metallocene-based polymerization initiators (hereinafter simply also referred to as "resin composition") to form a container, and a step of storing the container under temperature conditions of less than 0°C, wherein the i-line transmittance and the h-line transmittance of the storage container are both 1% or less. In the present invention, the container means a container filled with a resin composition.

[0012] According to the method for manufacturing a container of the present invention, the stability of the resin composition over time is improved. The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

[0013] Conventionally, the manufacture of a container filled with a resin composition containing a cyclic resin or a precursor thereof and a polymerization initiator has been carried out. Here, it has been found that a resin composition containing a cyclic resin or a precursor thereof has a large viscosity change over time. The viscosity change of a resin composition containing a cyclic resin or a precursor thereof has two types: a change in the direction of increasing viscosity (thickening) and a change in which the viscosity decreases (thinning). Thickening is considered to occur when the polymerization reaction of polymerizable groups contained in the cyclic resin or its precursor, polymerizable compounds, etc. partially proceeds due to the action of the polymerization initiator in the composition. Such thickening is remarkable when the composition contains at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator. Although the details of thinning are not clear, it is considered to occur when components such as acids and bases in the composition cleave the resin main chain or desorb the protecting group of the resin, causing the resin to partially become low molecular weight. In the present invention, it is considered that the thickening is suppressed by using a storage container for the container having an i-line transmittance and an h-line transmittance of 1% or less. Further, in the present invention, it is considered that by storing the container under temperature conditions of less than 0°C, cleavage of the resin main chain, elimination of the protecting group of the resin, etc. during storage are suppressed, and the above-mentioned viscosity reduction is also suppressed. As a result, according to the present invention, both thickening and viscosity reduction of the resin composition are suppressed, and the stability of the resin composition over time is improved.

[0014] In addition, in a resin composition containing a cyclic resin or a precursor thereof, in recent years, high-level resolution, realization of elongation, and suppression of coating defects have been demanded. As described above, in the present invention, it is considered that the polymerization reaction of the polymerizable group in the composition is suppressed from proceeding partially. Therefore, for example, in pattern formation by exposure and development, the resolution is considered to be improved for reasons such as improving the dissolution contrast. Specifically, there are cases where a part of the pattern is missing or a defect such as a breakage is suppressed. Furthermore, in the present invention, as described above, it is considered that the reduction in the molecular weight of the resin is suppressed. Therefore, the resolution is considered to be improved, such as the pattern (image part) remaining after development being difficult to be removed by development. Specifically, there are cases where the remaining film property after development is improved. Also, as described above, since the polymerization reaction of the polymerizable group in the composition is suppressed from proceeding partially, for example, in the case of a polyimide precursor, the imide cyclization during heating is suppressed from being inhibited by the polymer formed by the polymerization reaction. Therefore, the mechanical properties such as the elongation (e.g., breaking elongation) of the cured product are considered to be excellent. In addition, since the thickening and viscosity reduction of the resin composition are suppressed as described above, it is considered that coating defects are also suppressed. Furthermore, although the viscosity of the composition varies with temperature, it is considered that the viscosity at a low temperature below 0°C is higher than that at 25°C, for example. That is, in the storage step of the present invention, by storing at a temperature below 0°C, the viscosity can be temporarily stored in a high state. Thus, by temporarily increasing the viscosity during storage, liquid sloshing during storage is suppressed, and it is considered that the generation of bubbles in the composition due to liquid sloshing is also suppressed. For example, in the case of transporting while storing during storage, the effect of suppressing this liquid sloshing becomes remarkable. By suppressing the generation of these bubbles, it is considered that the occurrence of coating defects is suppressed. Hereinafter, the manufacturing method of the container of the present invention will be described in detail.

[0015] <Storage step> The manufacturing method of the container of the present invention includes a step of filling a storage container with a resin composition containing a resin that is a cyclic resin or its precursor, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator to obtain a container (also referred to as a "storage step"). Details of the resin composition will be described later.

[0016] 〔Storage container〕 The i-line transmittance and h-line transmittance of the storage container used in the storage step are both 1% or less. Here, the i-line transmittance and h-line transmittance are measured using a spectrophotometer (U-3900H manufactured by Hitachi High-Tech Science Corporation) on a fragment of the container body. The i-line transmittance and h-line transmittance of the storage container are preferably both 0.1% or less, and more preferably both 0.01% or less.

[0017] Also, the wall of the storage container preferably has two or more resin layers. Specifically, the storage container preferably has a resin layer that absorbs i-line and h-line, and another resin layer.

[0018] Examples of the resin layer that absorbs i-line and h-line include a resin layer containing at least one of a light-shielding pigment and an ultraviolet absorber. Examples of the light-shielding pigment include inorganic pigments such as titanium oxide, carbon black, red iron oxide, and silicon dioxide, and organic pigments such as phthalocyanine-based, quinacridone-based, and azo-based pigments. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers (such as phenyl salicylate and p-octylphenyl salicylate), benzophenone-based ultraviolet absorbers (such as 2,4-dihydroxybenzophenone and bis(2-methoxy-4-hydroxy-5-benzoyl-phenyl)methane), benzotriazole-based ultraviolet absorbers (such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole), and cyanoacrylate-based ultraviolet absorbers (such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and ethyl-2-cyano-3,3-diphenylacrylate).

[0019] The resin in the resin layer that absorbs i-line and h-line is not particularly limited, and examples include olefin resins such as polyethylene and polypropylene.

[0020] As another resin layer, a layer made of a resin having excellent solvent resistance is preferable. Examples of the resin having excellent solvent resistance include olefin resins, polyvinyl alcohol, poly(ethylene-co-vinyl alcohol), polyesters, and polyphenylene oxides. These resins can be selected and used according to the components of the solvent contained in the resin composition to be stored, for example, those that are difficult to dissolve in the resin composition to be stored.

[0021] In this case, for example, the layer in contact with the resin composition of the storage container can be a resin layer having excellent solvent resistance, and the layer not in contact with the resin composition of the storage container can be a resin layer that absorbs i-line and h-line. Alternatively, the wall of the storage container can be configured to have three layers: an inner layer (the layer in contact with the resin composition), an intermediate layer (the layer in contact with the inner layer and the outer layer, e.g., a gas barrier layer, etc.), and an outer layer (the outermost layer in contact with the intermediate layer). As the inner layer, for example, a layer made of a polymer of an olefin such as ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, or octene-1, or a copolymer of ethylene and another olefin can be used. As the intermediate layer, a layer containing at least one selected from the group consisting of polyamide, polyvinyl alcohol, poly(ethylene-co-vinyl alcohol), polyester, and polyphenylene oxide can be used. As the outer layer, a resin layer that absorbs the above-mentioned i-line and h-line can be used. Also, the storage container may be a storage container that only contains a resin layer that absorbs the i-line and h-line.

[0022] The wall thickness of the storage container (when the wall of the storage container has two or more resin layers, the total wall thickness thereof) is not particularly limited, but is preferably 0.5 mm or more, more preferably 1 mm or more, and even more preferably 1.5 mm or more. The upper limit is not particularly limited, but can be, for example, 1 cm or less.

[0023] The storage container preferably has a pouring spout. Also, it is preferable that the above-mentioned pouring spout can be covered with a lid. The diameter of the pouring spout of the storage container is not particularly limited, but is preferably 5 to 50 mm, more preferably 10 to 40 mm, and even more preferably 15 to 35 mm.

[0024] The internal volume of the storage container is not particularly limited, but is preferably 10 to 50,000 mL, more preferably 30 to 30,000 mL, and even more preferably 50 to 20,000 mL.

[0025] 〔Filling method〕 The filling method is not particularly limited, and known methods can be used. For example, filling by supplying the resin composition from a nozzle, filling by transferring the resin composition from another container to a storage container, etc. can be mentioned.

[0026] 〔Filling rate〕 The porosity represented by the following formula in the container is preferably 0.01 to 30% by volume, more preferably 0.1 to 20% by volume, still more preferably 1 to 15% by volume, and still more preferably 5 to 15% by volume. Porosity (%) = (1 - (volume of the resin composition in the container / capacity of the storage container)) x 100 Also, the gas contained in the voids is preferably air. Further, the moisture content contained in the above air is preferably 20 g / m 3 or less, more preferably 18 g / m 3 or less, and still more preferably 16 g / m 3 or less. The lower limit of the above moisture content is not particularly limited and may be 0. By setting the porosity to be equal to or higher than the above lower limit, due to the radical polymerization inhibition effect by oxygen, the polymerization of the polymerizable groups contained in the resin, polymerizable compound, etc. in the resin composition is suppressed, the thickening of the resin composition is suppressed, and the resolution is considered to be improved. Also, by setting the porosity to be equal to or lower than the above upper limit, it is considered that the generation of bubbles due to liquid sloshing is suppressed.

[0027] <Storage step> The method for manufacturing the container of the present invention includes a step of storing the container under temperature conditions of less than 0°C (also referred to as the "storage step"). In the storage step, the container is preferably sealed.

[0028] The storage temperature in the storage step is less than 0°C, preferably less than -5°C, more preferably less than -10°C, and still more preferably less than -15°C. The lower limit of the storage temperature may be set within a range where the resin composition does not freeze. For example, it is preferably -40°C or higher, more preferably -30°C or higher, and even more preferably -25°C or higher. The means for achieving the storage temperature is not particularly limited, and examples include known refrigeration equipment.

[0029] The storage in the storage step may be carried out under conditions where the container is exposed to light. Also, basically under light-shielding conditions, it may be under conditions where it is temporarily exposed to light during storage. Since both the i-line transmittance and h-line transmittance of the storage container in the present invention are 1% or less, it is considered that the photosensitivity (photosensitivity of the polymerization initiator) of the resin composition is suppressed even if it is exposed to light.

[0030] During storage in the storage step, for example, the container may be transported. According to the present invention, for example, even if liquid sloshing or the like occurs during transportation, it is considered that the occurrence of coating defects is suppressed due to a temporary increase in viscosity at low temperatures.

[0031] <Other steps> The method for manufacturing the container of the present invention may further include other steps different from the storage step and the accommodation step. Examples of other steps include a step of preparing the resin composition, a step of taking out the resin composition from the container, a step of setting the temperature of the container to 0°C or higher, and the like. The step of preparing the resin composition can be carried out by the method described in the preparation of the resin composition described later. In the step of taking out the resin composition from the container, for example, the resin composition can be taken out from the above-mentioned pouring port. The step of setting the temperature of the container to 0°C or higher is preferably carried out after the storage step, and preferably before the step of taking out the resin composition from the container after the storage step. After the step of setting the temperature of the container to 0°C or higher, in order to suppress thickening, thinning, etc. of the resin composition, it is preferable to promptly carry out the step of taking out the resin composition from the container. When the temperature of the container is set to 0 °C or higher, the temperature of the container may be increased using heating means, or the temperature of the container may be increased by allowing the container to stand at room temperature or the like. In the present invention, the resin composition can also be taken out at a temperature below 0 °C and used as it is, or the temperature of the resin composition can be raised to the use temperature immediately before use.

[0032] <Resin composition> The resin composition used in the present invention contains a resin that is a cyclized resin or a precursor thereof, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator.

[0033] The resin composition according to the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used for forming a film to be subjected to exposure and development using a developer containing an organic solvent. The resin composition according to the present invention can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer. Further, the resin composition according to the present invention is preferably used for forming a photosensitive film to be subjected to negative development. In the present invention, negative development refers to development in which the unexposed portion is removed by development in exposure and development, and positive development refers to development in which the exposed portion is removed by development. As the above exposure method, the above developer, and the above development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the development method described in the development step are used.

[0034] Further, the resin composition according to the present invention preferably contains a component having a polymerizable group. When the resin composition contains a component having a polymerizable group, the resin composition according to the present invention preferably satisfies at least one of the following (1) and (2). (1) As the above resin, a resin having a polymerizable group is included. (2) Further comprising a coincidence compound Moreover, as the polymerizable group, a radical polymerizable group is preferable.

[0035] <Specific resin> The resin composition according to the present invention contains at least one resin (specific resin) selected from the group consisting of a cyclized resin and its precursor. The cyclized resin preferably is a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain represents the relatively longest bond chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of the cyclized resin refers to a resin that undergoes a chemical structure change to become a cyclized resin upon external stimulation. A resin that undergoes a chemical structure change by heat to become a cyclized resin is preferable, and a resin that undergoes a ring closure reaction by heat to form a ring structure and thus becomes a cyclized resin is more preferable. Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, and the like. That is, the resin composition according to the present invention preferably contains, as the specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition according to the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition according to the present invention preferably contains a radical polymerization initiator described below, more preferably contains a radical polymerization initiator described below and a radical crosslinking agent described below. Further, if necessary, a sensitizer described below can be contained. From such a resin composition according to the present invention, for example, a negative photosensitive film is formed. Further, the specific resin may have a polarity-converting group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition according to the present invention preferably contains a photoacid generator described later. From such a resin composition according to the present invention, for example, a positive photosensitive film or a negative photosensitive film that is a chemically amplified type is formed.

[0036] 〔Polyimide precursor〕 The polyimide precursor used in the present invention is not particularly limited in terms of its type or the like, but preferably contains a repeating unit represented by the following formula (2).

Chemical formula

[0037] A 1 and A 2 in formula (2) each independently represents an oxygen atom or -NH-, and an oxygen atom is preferred. R 111represents 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 preferably 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 composed of a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The above linear or branched aliphatic group may be substituted with a group in which a hydrocarbon group in the chain contains a heteroatom, and the above cyclic aliphatic group and aromatic group may be substituted with a group in which a hydrocarbon group of the ring member contains a heteroatom. As a preferred embodiment according to the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and particularly preferably a group represented by -Ar-L-Ar-. However, Ar is independently an aromatic group, and 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-, -SO 2 - or -NHCO-, or a group composed of a combination of two or more of the above. These preferred ranges are as described above.

[0038] R 111 is preferably derived from a diamine. Examples of the diamine include the compounds described in paragraphs 0078 to 0088 of International Publication No. 2021 / 045126.

[0039] Also, R 111 preferably includes the structures described in paragraphs 0071 to 0077 of International Publication No. 2021 / 045126.

[0040] R 115 specifically includes tetracarboxylic acid residues remaining after removal of the anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one kind or two or more kinds of structures corresponding to R 115 . Examples of the tetracarboxylic dianhydride include the compounds described in paragraphs 0027 to 0031 of International Publication No. 2021 / 045126.

[0041] In formula (2), R 111 and R 115 may also have at least one OH group. More specifically, examples of R 111 include residues of bisaminophenol derivatives.

[0042] R in formula (2) 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Also, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenic 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. As the radically polymerizable group of the polyimide precursor, a group having an ethylenic unsaturated bond is preferable. Examples of the group having an ethylenic 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, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (III), etc., and a group represented by the following formula (III) is preferable.

[0043]

Chemical formula

[0044] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferable. In formula (III), * represents a bonding site with other structures. 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. Examples of preferred R 201 include alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, etc., a 1,2-butanediyl group, a 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy groups, including alkylene groups such as an ethylene group and a propylene group, -CH 2 CH(OH)CH 2 -, a cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as an ethylene group and a propylene group, or polyalkyleneoxy groups are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different from each other. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block-containing arrangement, or an arrangement having a pattern such as an alternating pattern. The carbon number of the above alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, even more preferably 2 to 5, yet even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Further, the above alkylene group may have a substituent. Preferred substituents include an alkyl group, an aryl group, a halogen atom, etc. In addition, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the repeating number of the polyalkyleneoxy group) is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 6. As the polyalkyleneoxy group, from the viewpoints of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged, may form blocks and be arranged, or may be arranged in an alternating pattern or the like. The preferable embodiments of the repeating numbers of ethyleneoxy groups and the like in these groups are as described above.

[0045] In formula (2), R 113 is a hydrogen atom, or R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0046] In formula (2), at least one of R 113 and R 114 may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

[0047] Further, the polyimide precursor may have a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 20% by mass or less.

[0048] Also, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there are exemplified modes using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0049] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one kind of the polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A)

Chemical formula

[0050] A 1 and A 2 and R 111 and R 113 and R 114 and R are each independently the same as A in formula (2), and the preferred ranges are also the same. 1 A 2 and R 111 and R 113 and R 114 and are the same as those in formula (2), and the preferred ranges are also the same. R 112 is the same as R in formula (5), and the preferred range is also the same. 112 and is the same as that in formula (5), and the preferred range is also the same.

[0051] The polyimide precursor may contain one kind of repeating unit represented by formula (2), or may contain two or more kinds. It may also contain structural isomers of the repeating unit represented by formula (2). Needless to say, the polyimide precursor may also contain other types of repeating units in addition to the repeating unit of the above formula (2).

[0052] As one embodiment of the polyimide precursor in the present invention, there is an embodiment in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyimide precursor excluding the terminals may be the repeating units represented by formula (2).

[0053] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. The dispersity of the molecular weight of the above polyimide precursor is preferably 1.0 to 7.0, more preferably 1.1 to 6.5, and still more preferably 1.2 to 6.0. In this specification, the polydispersity of the molecular weight is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and polydispersity of at least one polyimide precursor are within the above ranges. Also, it is preferable that the weight average molecular weight, number average molecular weight, and polydispersity calculated for the plurality of polyimide precursors as one resin are within the above ranges, respectively.

[0054] 〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23 °C in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium. From the viewpoint of pattern formability, it is preferably a polyimide that dissolves 0.5 g or more, and more preferably a polyimide that dissolves 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Also, from the viewpoints of the film strength and insulation of the obtained organic film, the polyimide preferably has a plurality of imide structures in the main chain. In this specification, the "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to the other bond chains.

[0055] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the main chain end or in the side chain, but it is preferably in the side chain. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by the following formula (4).132 or R in the repeating unit represented by formula (4) described later 131 is preferably included, and R in the repeating unit represented by formula (4) described later 132 or R in the repeating unit represented by formula (4) described later 131 is more preferably included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is preferably included in R in the repeating unit represented by formula (4) described later 131 and is more preferably included as a group having an ethylenically unsaturated bond in R in the repeating unit represented by formula (4) described later. 131 Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having a vinyl group which may be substituted and is directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having a vinyl group which may be substituted and is directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and the like.

[0056] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

Chemical formula

Chemical formula

Chemical formula

[0057] Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond, or a crosslinkable group other than the group having the above-mentioned ethylenically unsaturated bond. R 131 represents a divalent organic group. Examples of the divalent organic group are the same as those of R 111 in formula (2), and the preferable range is also the same. Also, examples of R 131 include a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cycloaliphatic or aromatic diamines. Specific examples include those of R 111 in formula (2) of the polyimide precursor.

[0058] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain, in terms of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more of either or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and still more preferably, it is the above-mentioned diamine and is a diamine residue not containing an aromatic ring.

[0059] Examples of the diamine containing two or more of either or both of an ethylene glycol chain and a propylene glycol chain in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above product names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but are not limited thereto.

[0060] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group are the same as those of R in formula (2), and the preferable ranges are also the same. 115 For example, the four bonds of the tetravalent organic group exemplified as R are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring. 115

[0061] Also, R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride, etc. Specific examples include those of R in formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 115 is preferably an aromatic diamine residue having 1 to 4 aromatic rings. 132

[0062] It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2 - bis(3 - hydroxy - 4 - aminophenyl)propane, 2,2 - bis(3 - hydroxy - 4 - aminophenyl)hexafluoropropane, 2,2 - bis(3 - amino - 4 - hydroxyphenyl)propane, 2,2 - bis(3 - amino - 4 - hydroxyphenyl)hexafluoropropane, the above (DA - 1) to (DA - 18) are preferable examples, and as R 132 , the above (DAA - 1) to (DAA - 5) are more preferable examples.

[0063] The weight - average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. By setting the weight - average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight - average molecular weight is particularly preferably 15,000 or more. Also, the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and still more preferably from 4,000 to 20,000. The dispersity of the molecular weight of the above polyimide is preferably from 1.0 to 7.0, more preferably from 1.1 to 6.5, and still more preferably from 1.2 to 6.0. When the resin composition contains a plurality of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide are within the above ranges. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the above plurality of polyimides as one resin are each within the above ranges.

[0064] 〔Polybenzoxazole precursor〕 The polybenzoxazole precursor used in the present invention is not particularly defined in terms of its structure or the like, but preferably contains a repeating unit represented by the following formula (3).

Chemical formula

[0065] In formula (3), R 123 and R 124 are each synonymous with R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0066] Examples of the dicarboxylic acid residue include the structures described in paragraphs 0086 to 0090 of International Publication No. 2021 / 006181.

[0067] In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same. Examples of R 122 include the structures described in paragraphs 0091 to 0101 of International Publication No. 2021 / 006181.

[0068] The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). The polybenzoxazole precursor preferably contains the repeating units and the like described in paragraphs 0102 to 0104 of International Publication No. 2021 / 006181 in terms of suppressing the occurrence of warping associated with ring closure.

[0069] The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The dispersity of the molecular weight of the above polybenzoxazole precursor is preferably 1.0 to 7.0, more preferably 1.1 to 6.5, and still more preferably 1.2 to 6.0. When the resin composition contains a plurality of types of polybenzoxazole precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polybenzoxazole precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the above plurality of types of polybenzoxazole precursors as one resin are each within the above ranges.

[0070] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. Further, it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group. [Chemical formula] In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group. When having a polarity conversion group such as a polymerizable group or an acid-decomposable group, the polarity conversion group such as a polymerizable group or an acid-decomposable group may be located at least on one of R 133 and R 134 , or may be located at the terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [Chemical formula] In formula (X-1), at least one of R 135 and R 136 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meaning as in formula (X). Formula (X-2) [Chemical formula] In formula (X-2), R 137 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups have the same meaning as in formula (X).

[0071] The polarity conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as the polymerizable group described for the polymerizable group possessed by the above polyimide precursor.

[0072] R133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group or an aromatic group. Specific examples include R in the formula (3) of the polybenzoxazole precursor 121 . Further, preferred examples thereof are the same as R 121 .

[0073] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor 122 . Further, preferred examples thereof are the same as R 122 . For example, the four bonds of the tetravalent organic group exemplified as R 122 are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is the following organic group, the following structure is formed. In the following structure, * represents the bonding site with the nitrogen atom or the oxygen atom in the formula (X) respectively.

Chemical formula

[0074] The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, the film shrinkage due to ring closure that occurs during oxazolization by heating is reduced, and the occurrence of warping can be more effectively suppressed. The above oxazolization rate is measured, for example, by the following method. Measure the infrared absorption spectrum of the polybenzoxazole, and obtain the peak intensity Q1 near 1650 cm -1 , which is the absorption peak derived from the amide structure of the precursor. Next, normalize it with the absorption intensity of the aromatic ring found near 1490 cm -1 . After heat-treating the polybenzoxazole at 350 °C for 1 hour, measure the infrared absorption spectrum again, obtain the peak intensity Q2 near 1650 cm -1 , and 1490 cm -1Normalize with the absorption intensity of the aromatic ring observed nearby. Using the normalized values of the obtained peak intensities Q1 and Q2, the oxazole formation rate of polybenzoxazole can be determined based on the following formula. Oxazole formation rate (%) = (Normalized value of peak intensity Q1 / Normalized value of peak intensity Q2) × 100

[0075] All polybenzoxazoles may contain a repeating unit of the above formula (X) containing one type of R 131 or R 132 and may also contain a repeating unit of the above formula (X) containing two or more different types of R 131 or R 132 In addition to the repeating unit of the above formula (X), polybenzoxazole may also contain other types of repeating units.

[0076] Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, and then oxazolizing it using a known oxazole formation reaction method. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used to increase the reaction yield and the like.

[0077] The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is within the above range. Also, the number average molecular weight (Mn) of the polybenzoxazole is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and still more preferably from 9,200 to 11,200. The polydispersity of the molecular weight of the above polybenzoxazole is preferably from 1.0 to 7.0, more preferably from 1.1 to 6.5, and still more preferably from 1.2 to 6.0. Also, when the resin composition contains a plurality of polybenzoxazoles as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and polydispersity of at least one polybenzoxazole are within the above ranges. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and polydispersity calculated for the plurality of polybenzoxazoles as one resin are each within the above ranges.

[0078] 〔Polyamideimide precursor〕 The polyamideimide precursor may contain a repeating unit represented by the following formula (PAI-2).

Chemical formula

[0079] In formula (PAI-2), R 117 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these with a single bond or a linking group, and 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 formed by combining two or more of these with a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms with a single bond or a linking group is more preferable. Examples of the above linking group include -O-, -S-, -C(=O)-, -S(=O) 2- An alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is even more preferred. Further, examples of the halogen atom in the above-mentioned halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like. As the above-mentioned arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is even more preferred.

[0080] Also, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. As the above-mentioned halogenation, chlorination is preferred. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups of the above-mentioned tricarboxylic acid compound may be acid anhydrified. Examples of the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched-chain aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0081] Specifically, as the tricarboxylic acid compound, 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 by a single bond or a linking group is preferable, and 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 by a single bond or a linking group is more preferable.

[0082] In formula (PAI-2), R 111 , A 2 , R 113 are respectively synonymous with R 111 , A 2 , R 113 in the above formula (2), and the preferred embodiments are also the same.

[0083] The polyamideimide precursor may further contain other repeating units. Examples of other repeating units include repeating units represented by formula (PAI-1) described in paragraph 0066 of International Publication No. 2020 / 262227.

[0084] In addition, specific examples of the dicarboxylic acid compound include compounds described in paragraph 0070 of International Publication No. 2020 / 262227. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the above dicarboxylic acid compound are halogenated.

[0085] In formula (PAI-1), R 111 is synonymous with R 111 in the above formula (2), and the preferred embodiments are also the same.

[0086] In addition, it is also preferable that the polyamideimide precursor has a fluorine atom in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0087] Further, for the purpose of improving the adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be mentioned.

[0088] As one embodiment of the polyamideimide precursor in the present invention, an embodiment in which the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units can be mentioned. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyamideimide precursor excluding the terminals may be any of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2). Also, as another embodiment of the polyamideimide precursor in the present invention, an embodiment in which the total content of the repeating unit represented by formula (PAI-2) and the repeating unit represented by formula (PAI-1) is 50 mol% or more of all the repeating units can be mentioned. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyamideimide precursor excluding the terminals may be either the repeating unit represented by formula (PAI-2) or the repeating unit represented by formula (PAI-1).

[0089] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The dispersity of the molecular weight of the polyamideimide precursor is preferably from 1.0 to 7.0, more preferably from 1.1 to 6.5, and still more preferably from 1.2 to 6.0. When the resin composition contains a plurality of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamideimide precursor are within the above ranges. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the plurality of polyamideimide precursors as one resin are each within the above ranges.

[0090] 〔Polyamideimide〕 The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer mainly composed of an organic solvent. In the present specification, the alkali-soluble polyamideimide means a polyamideimide that dissolves 0.1 g or more in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formability, it is preferably a polyamideimide that dissolves 0.5 g or more, and more preferably a polyamideimide that dissolves 1.0 g or more. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less. Further, from the viewpoints of the film strength and insulation properties of the obtained organic film, the polyamideimide preferably has a plurality of amide bonds and a plurality of imide structures in the main chain.

[0091] -Fluorine atom- From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has a fluorine atom. The fluorine atom is preferably contained in, for example, R in the repeating unit represented by the following formula (PAI-3) 117 , or R 111 and is more preferably contained as an alkyl fluoride group in R in the repeating unit represented by the following formula (PAI-3) 117 , or R 111 . The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0092] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond. The polyamideimide may have an ethylenically unsaturated bond at the main chain end or in the side chain, but it is preferably in the side chain. The above-mentioned ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 and more preferably contained as a group having an ethylenically unsaturated bond in R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 The preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide. The preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0093] The amount of the ethylenically unsaturated bond relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0094] -Polymerizable group other than ethylenically unsaturated bond- The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide. The polymerizable group other than the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the following formula (PAI-3), for example. 111 ​The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably from 0.05 to 10 mol / g, more preferably from 0.1 to 5 mol / g.

[0095] -Polarity conversion group- The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is the same as the acid-decomposable group described in R in the above formula (2) 113 and R 114 and the preferred embodiments are also the same.

[0096] -Acid value- When the polyamideimide is subjected to alkali development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. Further, the above acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and still more preferably 200 mgKOH / g or less. When the polyamideimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamideimide is preferably from 2 to 35 mgKOH / g, more preferably from 3 to 30 mgKOH / g, and still more preferably from 5 to 20 mgKOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Examples of the acid groups contained in the polyamideimide include the same groups as the acid groups in the above polyimide, and the preferred embodiments are also the same.

[0097] -Phenolic hydroxy group- From the viewpoint of making the development rate with an alkali developer appropriate, the polyamideimide preferably has a phenolic hydroxy group. The polyamideimide may have phenolic hydroxy groups at the main chain terminals or at the side chains. The phenolic hydroxy groups are preferably included, for example, in R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 and are preferably included in. The amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0098] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it may contain a repeating unit represented by the following formula (PAI-3).

Chemical formula

[0099] Also, in order to improve the storage stability of the resin composition, the polyamideimide is preferably sealed at the main chain terminals with a terminal sealing agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. The preferred embodiments of the terminal sealing agent are the same as the preferred embodiments of the terminal sealing agent in the above-mentioned polyimide.

[0100] -Imidization rate (ring closure rate)- The imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more from the viewpoints of the film strength, insulation, etc. of the obtained organic film. The upper limit of the imidization rate is not particularly limited and may be 100% or less. The imidization rate is measured by the same method as the ring closure rate of the above polyimide.

[0101] The polyamideimide may contain repeating units represented by the above formula (PAI-3) all of which contain one type of R111 or R117, or may contain repeating units represented by the above formula (PAI-3) that contain two or more different types of R131 or R132. Further, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0102] The polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by stopping the imidization reaction halfway to introduce a partial imide structure, or further by blending a completely imidized polymer with its polyamideimide precursor to introduce a partial imide structure.

[0103] The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Also, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The dispersity of the molecular weight of the polyamideimide is preferably 1.0 to 7.0, more preferably 1.1 to 6.5, and even more preferably 1.2 to 6.0. When the resin composition contains a plurality of polyamide-imides as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide are within the above ranges. Also, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the above plurality of polyamide-imides as one resin are each within the above ranges.

[0104] 〔Method for producing polyimide precursor, etc.〕 Polyimide precursors, etc. can be obtained, for example, by a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid and then esterifying it using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine and a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine, etc. Among the above production methods, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine is more preferable. Examples of the above condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. Examples of the above alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the above halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. In the method for producing a polyimide precursor, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately determined according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and the like. In the production method of 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 according to the raw materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, and the like.

[0105] -Terminal capping agent- In the production method of a polyimide precursor or the like, in order to further improve the storage stability, the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like may be capped. In that case, when capping the carboxylic anhydride and anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, and the like. From the viewpoint of reactivity and film stability, it is more preferable to use monoalcohol, phenols, or monoamine. Examples of the terminal capping agent include the compounds described in paragraph 0090 of International Publication No. 2021 / 045126. Further, a plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents. Also, when sealing the amino group at the resin terminal, it is possible to seal it with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for the amino group are preferably carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and carboxylic acid anhydrides and carboxylic acid chlorides are more preferred. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. Also, preferred compounds of carboxylic acid chlorides include the compounds described in paragraph 0090 of International Publication No. 2021 / 045126, etc. etc. can be mentioned.

[0106] -Solid precipitation- In the production of polyimide precursors, etc., a step of precipitating a solid may be included. Specifically, after filtering off the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution as necessary, the obtained polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof, and the polymer component is precipitated to precipitate as a solid and dried to obtain a polyimide precursor, etc. In order to improve the purification degree, operations such as redissolving, reprecipitating, and drying the polyimide precursor, etc. may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[0107] 〔Content〕 The content of the specific resin in the resin composition according to the present invention is more preferably 3% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and even more preferably 8% by mass or more and 70% by mass or less. The resin composition according to the present invention may contain only one kind of specific resin or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0108] 〔Polymerization initiator〕 The resin composition according to the present invention contains at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator. Examples of the oxime-based polymerization initiator 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), compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc. The contents are incorporated herein.

[0109] Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxypentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition according to the present invention, it is particularly preferable to use an oxime compound (an oxime-based photo radical polymerization initiator) as the photo radical polymerization initiator. The oxime-based photo radical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0110] [Chem.]

[0111] In commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by Adeka Corporation, photoinitiator 2 described in JP-A-2012-014052) are also preferably used. Further, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831 and Adeka Arcles NCI-930 (manufactured by Adeka Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemical Co., Ltd.), SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Further, an oxime compound having the following structure can also be used. [Chem.]

[0112] As the photoinitiator for radical polymerization, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466 and Patent 06636081, the contents of which are incorporated herein.

[0113] As the photoinitiator for radical polymerization, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in WO 2013 / 083505, the contents of which are incorporated herein.

[0114] In addition, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, etc. This content is incorporated herein.

[0115] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249, paragraph numbers 0008 to 0012, 0070 to 0079 of JP-A-2014-137466, and the compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071. This content is incorporated herein. In addition, as the oxime compound having a nitro group, Adeka Arcles NCI-831 (manufactured by ADEKA CORPORATION) is also included.

[0116] As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0117] As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019 / 088055, and this content is incorporated herein.

[0118] As the photopolymerization initiator, an oxime compound (hereinafter also referred to as oxime compound OX) having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into the aromatic ring can also be used. The above aromatic ring group Ar OX1Examples of the electron-withdrawing group include an acyl group, nitro group, trifluoromethyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it easily forms a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, cyano group, nitro group, hydroxy group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group, or amino group. An alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, or amino group is more preferred, and an alkoxy group, alkylsulfanyl group, or amino group is even more preferred.

[0119] The oxime compound OX is preferably at least one selected from the compound represented by formula (OX1) and the compound represented by formula (OX2), and more preferably the compound represented by formula (OX2).

Chemical formula

[0120] In the above formula, it is preferable that R X12 is an electron-withdrawing group and R X10 , R X11 , R X13 , R X14 are hydrogen atoms.

[0121] Specific examples of the oxime compound OX include the compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4600600, the content of which is incorporated herein.

[0122] Most preferably, the oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061, the content of which is incorporated herein.

[0123] From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone 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 benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivatives, a cyclopentadiene-benzene-iron complex and its salt, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound.

[0124] Examples of the metallocene-based polymerization initiator include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0125] Among these, it is preferable that the polymerization initiator contains at least one of the compounds represented by any of the following formulas (D-1) to (D-11).

Chemical formula

[0126] In addition, as the polymerization initiator, in addition to the above oxime-based polymerization initiator or the above metallocene-based polymerization initiator, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, organic boron compounds, iron arene complexes, etc. may be further included. Regarding the details of these, the descriptions in paragraphs 0165 to 0182 of JP-A No. 2016-027357 and paragraphs 0138 to 0151 of WO 2015 / 199219 can be referred to, and this content is incorporated herein. Also, the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, Patent No. 6301489, the peroxide-based photoinitiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photoinitiators described in WO 2018 / 221177, the photoinitiators described in WO 2018 / 110179, the photoinitiators described in JP-A No. 2019-043864, the photoinitiators described in JP-A No. 2019-044030, and the peroxide-based initiators described in JP-A No. 2019-167313 are mentioned, and the contents of these are also incorporated herein.

[0127] The content of the photoinitiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.3 to 15% by mass, and even more preferably 0.3 to 10% by mass, based on the total solid content of the resin composition according to the present invention. The photoinitiator may contain only one kind or two or more kinds. When two or more kinds of photoinitiators are contained, the total amount is preferably within the above range. Note that since the photoinitiator may function as a thermal polymerization initiator, crosslinking by the photoinitiator may further proceed by heating with an oven, a hot plate, or the like.

[0128] 〔Sensitizer〕 The resin composition preferably contains a sensitizer. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., and actions such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. As the sensitizer that can be used, compounds such as 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, indigo-based compounds can be used. Examples of the sensitizer include the compounds described in paragraph 0269 of International Publication No. 2021 / 045126. Also, other sensitizing dyes may be used. Regarding the details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP-A No. 2016-027357 can be referred to, and this content is incorporated herein.

[0129] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0130] [Chain transfer agent] The resin composition according to the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Third Edition of the Polymer Dictionary (edited by the Polymer Society, 2005). Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, dithiobenzoates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, trithiocarbonates, dithiocarbamates, xanthate compounds, etc. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, thiol compounds can be preferably used.

[0131] In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and this content is incorporated herein.

[0132] When the resin composition according to the present invention has 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 still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition according to the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is within the above range.

[0133] [Polymerizable compound] The resin composition according to the present invention preferably contains a polymerizable compound. Examples of the crosslinking compound include a radical crosslinking agent or other crosslinking agents.

[0134] 〔Radical crosslinking agent〕 The resin composition according to the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, as the group containing an ethylenically unsaturated bond, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

[0135] 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. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is still more preferable. Also, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition according to the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0136] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0137] Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof. Preferably, they are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. are also preferably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and further, substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, instead of the above unsaturated carboxylic acids, it is also possible to use a group of compounds replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can refer to the descriptions in paragraphs 0113 to 0122 of JP-A-2016-027357, and these contents are incorporated herein.

[0138] In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerin and trimethylolethane and then (meth)acryloylating them, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-B-52-030490, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

[0139] In addition, as other preferred radical crosslinking agents, compounds having a fluorene ring and having two or more groups having an ethylenically unsaturated bond, and cardo resins described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216, etc. can also be used.

[0140] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. Sho 46-043946, Japanese Patent Publication No. Hei 01-040337, Japanese Patent Publication No. Hei 01-040336, vinylphosphonic acid compounds described in Japanese Unexamined Patent Application Publication No. Hei 02-025493, etc. can be mentioned. Compounds containing a perfluoroalkyl group described in Japanese Unexamined Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

[0141] In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and the contents thereof are incorporated herein.

[0142] Also, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acryloylating them, which are described together with their specific examples as formula (1) and formula (2) in Japanese Unexamined Patent Application Publication No. Hei 10-062986, can also be used as a radical crosslinking agent.

[0143] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Unexamined Patent Application Publication No. 2015-187211 can also be used as a radical crosslinking agent, and the contents thereof are incorporated herein.

[0144] Examples of the radical crosslinking agent include dipentaerythritol triacrylate (commercially available as KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.; A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue is preferable. These oligomer types can also be used.

[0145] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having 4 ethyleneoxy chains, manufactured by Sartomer Co., SR-209, 231, 239, bifunctional methacrylates having 4 ethyleneoxy chains, manufactured by Sartomer Co., DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Brenmer PME400 (manufactured by NOF Corporation), and the like.

[0146] As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. Sho 48-041708, Japanese Unexamined Patent Application Publication No. Sho 51-037193, Japanese Examined Patent Publication No. Hei 02-032293, and Japanese Examined Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Examined Patent Publication No. Hei 62-039417, and Japanese Examined Patent Publication No. Hei 62-039418 are also suitable. Further, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Unexamined Patent Application Publication No. Sho 63-277653, Japanese Unexamined Patent Application Publication No. Sho 63-260909, and Japanese Unexamined Patent Application Publication No. Hei 01-105238 can also be used.

[0147] 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 having an acid group formed by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferably, in the radical crosslinking agent having an acid group formed by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Commercially available products include, for example, M-510, M-520, etc. as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0148] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. If the acid value of the radical crosslinking agent is within the above range, it is excellent in handling during production, and further, it is excellent in developability. Also, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

[0149] From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, modified dimethacrylate of isocyanuric acid, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. These can be mixed and used in combination of two or more as needed. Note that, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of the polyethylene glycol chain of about 200. From the perspective of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), as the radical crosslinking agent, a monofunctional radical crosslinking agent can preferably be used in the resin composition according to the present invention. Examples of the monofunctional radical crosslinking agent 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. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 °C or higher under normal pressure is also preferable in order to suppress volatilization before exposure. In addition, examples of the polyfunctional radical crosslinking agent having two or more functional groups include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0150] When containing a radical crosslinking agent, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition according to the present invention. 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.

[0151] The radical crosslinking agent may be used alone or in combination of two or more. When two or more are used in combination, it is preferable that the total amount is within the above range.

[0152] 〔Other Crosslinking Agents〕 The resin composition according to the present invention preferably contains other crosslinking agents different from the above-described radical crosslinking agents. Examples of the other crosslinking agents include the compounds described in paragraphs 0209 to 0222 of International Publication No. 2021 / 006181.

[0153] <Base Generator> The resin composition according to the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition according to the present invention include thermal base generators and photo base generators. In particular, when the resin composition contains a precursor of a cyclic resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. For example, the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package becomes good. The base generator may be an ionic base generator or a non-ionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. There is no particular limitation on the base generator according to the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Examples of the base generator include compounds corresponding to base generators among the onium salts described in paragraphs 0201 to 0231 of International Publication No. 2021045126, or thermal base generators described in paragraphs 0232 to 0246.

[0154] When the resin composition according to the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition according to the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. One kind or two or more kinds of base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0155] <Solvent> The resin composition according to the present invention preferably contains a solvent. As the solvent, known solvents can be arbitrarily used. 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.

[0156] As esters, for example, 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 alkoxyacetates (e.g., methyl alkyl alkoxyacetate, ethyl alkyl alkoxyacetate, butyl alkyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferably exemplified.

[0157] As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, 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, dipropylene glycol dimethyl ether, etc. can be mentioned as suitable ones.

[0158] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. can be mentioned as suitable ones.

[0159] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and cyclic terpenes such as limonene can be mentioned as suitable ones.

[0160] As sulfoxides, for example, dimethyl sulfoxide can be mentioned as a suitable one.

[0161] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0162] Examples of ureas include N,N,N’,N’-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0163] 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, methylphenylcarbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol, etc.

[0164] From the perspective of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[0165] 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, and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone, or a mixed solvent composed of two or more thereof is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone, or a combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Among these, the resin composition according to the present invention preferably contains at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and ethyl lactate as a solvent.

[0166] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid content concentration of the resin composition according to the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

[0167] The resin composition according to the present invention may contain only one kind of solvent or two or more kinds of solvents. When two or more kinds of solvents are contained, the total thereof is preferably within the above range.

[0168] <Metal Adhesion Improver> The resin composition according to the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used for 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 and a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, and the like.

[0169] 〔Silane coupling agent〕 Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573. The contents of these are incorporated herein. Further, as described in paragraphs 0050 to 0058 of JP-A-2011-128358, it is also preferable to use two or more different silane coupling agents. Further, it is also preferable to use the following compound as the silane coupling agent. In the following formulae, Me represents a methyl group and Et represents an ethyl group.

[0170]

Chemical formula

[0171] Examples of other silane coupling agents include 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-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0172] Aluminum-based adhesion promoter Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

[0173] In addition, as other metal adhesion improvers, 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 can also be used, and the contents thereof are incorporated herein.

[0174] 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 still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it to be not less than the above lower limit value, the adhesion between the pattern and the metal layer becomes good, and by setting it to be not more than the above upper limit value, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is within the above range.

[0175] <Migration inhibitor> The resin composition according to the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

[0176] The migration inhibitor is not particularly limited, but examples include compounds having a heterocyclic ring (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 and 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, 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, 5-amino-1H-tetrazole can be preferably used.

[0177] Alternatively, an ion trap agent that captures anions such as halogen ions can also be used.

[0178] Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, compounds described in paragraph 0052 of JP-A-2011-059656, compounds described in paragraphs 0114, 0116, and 0118 of JP-A-2012-194520, compounds described in paragraph 0166 of WO 2015 / 199219, etc., and the contents thereof are incorporated herein.

[0179] Specific examples of the migration inhibitor include compounds described in paragraph 0281 of WO 2020 / 262227, etc.

[0180] When the resin composition according to the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition according to the present invention.

[0181] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total thereof is preferably within the above range.

[0182] <Polymerization inhibitor> The resin composition according to 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, metal compounds, etc.

[0183] Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium(I) salt, N-nitros-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 can also be used, and this content is incorporated herein.

[0184] When the resin composition according to the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.01 to 10% by mass, based on the total solid content of the resin composition according to the present invention.

[0185] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total thereof is preferably within the above range.

[0186] <Other Additives> The resin composition according to the present invention may contain various additives, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (such as defoamers, flame retardants, etc.) as necessary within the range where the effects according to the present invention can be obtained. Further, a known acid scavenger may be included. By appropriately containing these components, properties such as film physical properties can be adjusted. These components can refer to the descriptions in, for example, paragraphs 0183 et seq. of JP-A-2012-003225 (paragraph numbers 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, and the contents of these are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition according to the present invention.

[0187] 〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0188] By incorporating a surfactant into the resin composition according to the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when forming a film using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is improved. Therefore, it is possible to more suitably form a film having a uniform thickness with little thickness unevenness.

[0189] Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Limited), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like. As the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used, and the contents thereof are incorporated herein. A block polymer can also be used as the fluorosurfactant, and specific examples include, for example, the compounds described in JP-A-2011-89090, and the contents thereof are incorporated herein. As the fluorosurfactant, a fluorine-containing polymer compound 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 an ethyleneoxy group or a propyleneoxy group) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [Chemical]

[0190] The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the content of which is incorporated herein. Commercially available products include, for example, Megafac RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation.

[0191] The fluorine content in the fluorosurfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. The fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid-saving property, and also has good solubility in the composition.

[0192] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie GmbH), etc.

[0193] Examples of hydrocarbon surfactants include, for example, Ionin A-76, New Calgen FS-3PG, Ionin B-709, Ionin B-811-N, Ionin D-1004, Ionin D-3104, Ionin D-3605, Ionin D-6112, Ionin D-2104-D, Ionin D-212, Ionin D-931, Ionin D-941, Ionin D-951, Ionin E-5310, Ionin P-1050-B, Ionin P-1028-P, Ionin P-4050-T, etc. (manufactured by Takemoto Yushi Co., Ltd.), and the like.

[0194] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Ionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0195] Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

[0196] Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

[0197] Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0198] [Higher fatty acid derivatives] In order to prevent polymerization inhibition caused by oxygen, the resin composition according to the present invention may add higher fatty acid derivatives such as behenic acid or behenic acid amide and unevenly distribute them on the surface of the resin composition according to the present invention during the drying process after coating.

[0199] Also, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015 / 199219 can be used, and this content is incorporated herein.

[0200] When the resin composition according to the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition according to the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more higher fatty acid derivatives, the total is preferably within the above range.

[0201] [Thermal polymerization initiator] The resin composition according to the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be advanced, so that the solvent resistance can be further improved. In addition, the above-described photoinitiator may also have a function of initiating polymerization by heat and may be added as a thermal polymerization initiator in some cases.

[0202] As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554 can be mentioned, and the content thereof is incorporated herein.

[0203] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass with respect to the total solid content of the resin composition according to the present invention. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0204] 〔Inorganic particles〕 The resin composition according to the present invention may contain inorganic fine particles. As the inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

[0205] The average particle diameter of the above inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the fine particles is the primary particle diameter and also the volume average particle diameter. The volume average particle diameter can be measured by the dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurement is difficult, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, or the laser diffraction / scattering method.

[0206] 〔Ultraviolet absorber〕 The composition according to the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate, etc. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0207] Examples of the substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, examples of the triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine, and the like.

[0208] In the present invention, each of the above various ultraviolet absorbers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an ultraviolet absorber. When it contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition according to the present invention.

[0209] [Organic Titanium Compound] The resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0210] Examples of 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 the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like. II) Tetraalkoxytitanium compound: 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}], and the like. III) Titanocene compound: 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, and the like. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctyl phosphate) 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, isopropyltridodecylbenzenesulfonyl titanate, etc.

[0211] Among them, as the organic titanium compound, it is preferable that it is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds from the viewpoint of exhibiting better chemical resistance. 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 preferable.

[0212] When blending an organic titanium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0213] 〔Antioxidant〕 The composition according to the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the film after curing and the adhesion to a metal material can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, thioether compounds, etc. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Further, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, a phosphorus-based antioxidant can also be preferably used. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzod[f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzod[f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, etc. Commercially available products of the antioxidant include, for example, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (the above are manufactured by ADEKA CORPORATION), etc. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and this content is incorporated herein. Further, the composition according to the present invention may contain a latent antioxidant as needed. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected by a protecting group, and the protecting group is eliminated by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid / base catalyst to function as an antioxidant.Examples of the potential anti-oxidant include the compounds described in International Publication No. WO2014 / 021023, International Publication No. WO2017 / 030005, and JP-A-2017-008219, the content of which is incorporated herein. Examples of commercially available products of the potential anti-oxidant include Adeka Arcles GPA-5001 (manufactured by ADEKA CORPORATION). Examples of preferred anti-oxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by the formula (3).

[0214]

Chemical formula

[0215] In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0216] The compound represented by the formula (3) suppresses the oxidative degradation of the aliphatic group and phenolic hydroxy group of the resin. Further, the rust prevention action on the metal material can suppress metal oxidation.

[0217] Since it can act on both the resin and the metal material simultaneously, an integer k of 2 to 4 is more preferable. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, etc., and it may further have a substituent. Among these, from the viewpoints of solubility in a developer and adhesion to a metal, it is preferable to have an alkyl ether group and -NH-, and -NH- is more preferable from the viewpoints of interaction with the resin and adhesion to the metal due to metal complex formation.

[0218] Examples of the compound represented by the general formula (3) include, but are not limited to, the following structures.

[0219]

Chemical formula

[0220]

Chemical formula

[0221]

Chemical formula

[0222]

Chemical formula

[0223] The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 part by mass or more, the effects of improving the elongation characteristics and adhesion to the metal material can be easily obtained even in a high-temperature and high-humidity environment. Also, by setting it to 10 parts by mass or less, for example, due to the interaction with the photosensitizer, the sensitivity of the resin composition is improved. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that their total amount is within the above range.

[0224] Anti - aggregating agent The resin composition of this embodiment may contain an anti - aggregating agent as needed. Examples of the anti - aggregating agent include sodium polyacrylate and the like.

[0225] In the present invention, the anti - aggregating agent may be used alone or in combination of two or more kinds. The composition according to the present invention may or may not contain an anti - aggregating agent. When it contains an anti - aggregating agent, the content of the anti - aggregating agent is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition according to the present invention.

[0226] Phenolic compound The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis - Z, BisP - EZ, TekP - 4HBPA, TrisP - HAP, TrisP - PA, BisOCHP - Z, BisP - MZ, BisP - PZ, BisP - IPZ, BisOCP - IPZ, BisP - CP, BisRS - 2P, BisRS - 3P, BisP - OCHP, methylene tris - FR - CR, BisRS - 26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP - PC, BIR - PC, BIR - PTBP, BIR - BIPC - F (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), etc.

[0227] In the present invention, the phenolic compound may be used alone or in combination of two or more kinds. The composition according to the present invention may or may not contain a phenolic compound. When it contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition according to the present invention.

[0228] Other polymer compounds Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified products into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups are introduced.

[0229] In the present invention, the other polymer compounds may be used alone or in combination of two or more. The composition according to the present invention may or may not contain other polymer compounds. When contained, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition according to the present invention.

[0230] <Properties of the resin composition> The viscosity of the resin composition according to the present invention can be adjusted by the solid content concentration of the resin composition. The viscosity (viscosity when filling the storage container) of the resin composition according to the present invention is preferably 50 to 5,000 cp, more preferably 75 to 4,500 cp, and even more preferably 100 to 4,000 cp. In particular, when the resin composition according to the present invention is used for slit coating, the viscosity of the resin composition is preferably 50 to 5,000 cp, more preferably 50 to 4,000 cp, and even more preferably 50 to 3,000 cp. The above viscosity is the value at 25°C. By setting the viscosity within the above range, a thinner cured film can be obtained. Further, according to the method for producing the container of the present invention, even when such a resin composition having a low viscosity is used, the viscosity reduction of the composition is suppressed, and the generation of bubbles during storage is suppressed. Therefore, it is considered that the occurrence of coating defects is suppressed. As described above, the polyimide for slit coating has a particularly low viscosity. In the method for manufacturing the container of the present invention, it is considered that the occurrence of coating defects is suppressed even when such a low-viscosity resin composition is used.

[0231] <Restrictions on the substances contained in the resin composition> The water content of the resin composition according to the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0232] From the viewpoint of insulation, the metal content of the resin composition according to the present invention is preferably less than 5 ppm (parts per million) by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., excluding metals contained as complexes of organic compounds and metals. When a plurality of metals are contained, the total of these metals is preferably within the above range.

[0233] In addition, examples of the method for reducing metal impurities unintentionally contained in the resin composition according to the present invention include selecting a raw material with a low metal content as the raw material constituting the resin composition according to the present invention, performing filter filtration on the raw material constituting the resin composition according to the present invention, and performing distillation under conditions where the inside of the apparatus is lined with polytetrafluoroethylene or the like to suppress contamination as much as possible.

[0234] When considering the use as a semiconductor material, the resin composition according to the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and still more preferably less than 200 ppm by mass from the viewpoint of wiring corrosiveness. Among them, those present in the state of halogen ions preferably have a content of less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom, or the total of the chlorine ion and the bromine ion is within the above range, respectively. As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferably mentioned.

[0235] <Cured product of resin composition> By curing the resin composition according to the present invention, a cured product of this resin composition can be obtained. The cured product according to the present invention is a cured product obtained by curing the resin composition according to the present invention. The curing of the resin composition is preferably by heating, more preferably within a range of 120°C to 400°C, still more preferably within a range of 140°C to 380°C, and particularly preferably within a range of 170°C to 350°C. 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 form, rod form, spherical form, pellet form, etc. In the present invention, this cured product is preferably in film form. Further, by pattern processing of the resin composition, the shape of this cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat dissipation function. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. When the resin composition according to the present invention is cured, the shrinkage rate is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after the curing of the resin composition, and can be calculated from the following formula. Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0236] <Properties of the cured product of the resin composition> The imidization reaction rate of the cured product of the resin composition according to the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, a cured product excellent in mechanical properties may be obtained. The elongation at break of the cured product of the resin composition according to the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition according to the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

[0237] <Preparation of the resin composition> The resin composition according to the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by a conventionally known method. Mixing can employ mixing by stirring blades, mixing by a ball mill, mixing by rotating the tank itself, etc. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0238] In addition, for the purpose of removing foreign matters such as dust and fine particles in the resin composition according to the present invention, it is preferable to perform filtration using a filter. Examples of the filter pore diameter include those of 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be combined for use. As a connection mode, for example, there is a mode in which an HDPE filter with a pore diameter of 1 μm is connected in series as the first stage and an HDPE filter with a pore diameter of 0.2 μm is connected in series as the second stage. Also, various materials may be filtered multiple times. When filtering multiple times, it may be a circulation filtration. Also, filtration may be performed under pressure. When performing filtration under pressure, examples of the pressure for pressurization include those of 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less. In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. A combination of filter filtration and an impurity removal treatment using an adsorbent may also be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after filtration using a filter, the resin composition filled in a bottle may be placed under reduced pressure and subjected to a degassing step.

[0239] (Storage method of resin composition) The storage method of the resin composition of the present invention is a storage method in which a resin composition containing a resin which is a cyclic resin or its precursor, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator is stored in a storage container, wherein the i-line transmittance and the h-line transmittance of the storage container are both 1% or less, and the storage is performed under temperature conditions of less than 0°C.

[0240] The resin composition in the method for storing the resin composition according to the present invention is the same as the resin composition used in the method for manufacturing the container of the present invention described above, and the preferred embodiments are also the same. Details of the storage method and storage container according to the present invention are the same as those of the storage method and storage container in the storage step included in the method for manufacturing the container of the present invention described above, and the preferred embodiments are also the same.

[0241] (Method for manufacturing a cured product) The method for manufacturing a cured product according to the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. The resin composition used in the method for manufacturing a cured product according to the present invention is a resin composition filled in a container obtained by the method for manufacturing a container of the present invention, or a resin composition stored by the method for storing a resin composition of the present invention. Furthermore, the method for manufacturing a cured product according to the present invention more preferably includes the above film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern. The method for manufacturing a cured product according to the present invention particularly preferably includes at least one of the above film forming step, the above exposure step, the above development step, a heating step of heating the pattern obtained by the development step, and a post-exposure step of exposing the pattern obtained by the development step. Furthermore, the manufacturing method according to the present invention preferably includes the above film forming step and a step of heating the above film. The method for manufacturing a cured product according to the present invention can be carried out with reference to known methods such as those described in paragraphs 0314 to 0354 of International Publication No. 2020 / 262227.

[0242] (Method for manufacturing a semiconductor device) The present invention also discloses a semiconductor device including a cured product according to the present invention or a laminate according to the present invention. The present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product according to the present invention or a method for manufacturing a laminate according to the present invention. As a specific example of a semiconductor device using the resin composition according to the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-027357 can be referred to, and these contents are incorporated herein.

Examples

[0243] The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed 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. "Parts" and "%" are based on mass unless otherwise specified.

[0244] <Synthesis of PI Precursor - 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 a temperature of 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, and while maintaining the temperature at -10 ± 5°C, 17.0 g of thionyl chloride was added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, a solution prepared by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10 ± 5°C over 60 minutes, 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, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate after stirring (solid of polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate after stirring (solid of polyimide precursor) was filtered again and dried under reduced pressure at 45 °C for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto and stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate 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 PI precursor-1. The weight average molecular weight of PI precursor-1 was 22,000. Also, PI precursor-1 is a resin containing a repeating unit having the following structure. [Chemical formula]

[0245] [Synthesis of PI precursor-2] While removing moisture in a dry reactor equipped with a flat-bottom joint with a stirrer, a condenser and an internal thermometer, 18.98 g (64.5 mmol) of 4,4'-biphenyl dianhydride was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 °C for 18 hours. Then, after cooling the mixture to -20 °C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Subsequently, the mixture was warmed to room temperature and stirred for 2 hours. Then, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Next, a solution prepared by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise to the obtained clear solution over 1 hour. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Subsequently, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 °C for 3 days to obtain PI precursor-2. When the molecular weight of PI precursor-2 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 10,000. PI precursor-2 is a resin containing the following repeating unit.

Chemical formula

[0246] <Synthesis of PI precursor-3> In the synthesis of PI precursor-2, synthesis was carried out in the same manner as for PI precursor-2, except that 4,4'-biphthalic anhydride was changed to 4,4'-oxydiphthalic anhydride and 4,4'-biphthalic anhydride, to obtain PI precursor-3. The total molar amount of 4,4'-oxydiphthalic anhydride and 4,4'-biphthalic anhydride was the same as the molar amount of 4,4'-biphthalic anhydride in the synthesis of PI precursor-2, and the molar ratio of 4,4'-oxydiphthalic anhydride to 4,4'-biphthalic anhydride was 1:1. When the molecular weight of PI precursor-3 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 22,000. PI precursor-3 is a resin containing the following two repeating units. [Chemical]

[0247] [Synthesis of PBO] 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and while maintaining the temperature at -10 to 0 °C, a solution prepared by dissolving 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride in 75 g of N-methylpyrrolidone was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added and stirring was continued for another 60 minutes. Then, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Then, the obtained polybenzoxazole precursor was dried under reduced pressure at 45 °C for 3 days to obtain PBO.

[0248] [Synthesis of Cyclized PI] While removing moisture in a dry reactor equipped with a flat-bottom joint fitted with a stirrer, a condenser, and an internal thermometer, 65.56 g (179 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.48 g (10 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 300 g of N-methylpyrrolidone (NMP). Subsequently, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added and stirred at a temperature of 40 °C for 2 hours. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added and stirred at 40 °C for 2 hours. After stirring, while flowing nitrogen at a flow rate of 200 ml / min, the temperature was raised to 180 °C and stirred for 6 hours. After cooling the above reaction solution to 25 °C, 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise, and after stirring at 25 °C for 2 hours, it was further stirred at 60 °C for 3 hours. This was cooled to 25 °C, 10 g of acetic acid was added, and it was stirred at 25 °C for 1 hour. After stirring, it was precipitated in 2 liters of water / methanol = 75 / 25 (volume ratio) and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was obtained by filtration, washed with 1.5 liters of water, then the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain polyimide. The obtained polyimide was dried under reduced pressure at 40 °C for 1 day to obtain a ring-closed PI.

[0249] <Examples and Comparative Examples> In each of the examples, the components described in the following table were mixed respectively to obtain each resin composition. Also, in each of the comparative examples, the components described in the following table were mixed respectively to obtain each comparative composition. Specifically, the content (blending amount) of each component described in the table other than the solvent was the numerical value (parts by mass) described in each column in the "Composition" of the table. The content (blending amount) of the solvent was adjusted so that the solid content concentration of the composition was the value (% by mass) of "Solid Content Concentration (%)" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was the ratio according to the numerical value described in each column in the "Solvent" of the table. The obtained resin composition and comparative composition were pressure-filtered using a first filter made of polyethylene with a pore width of 1.0 μm and a second filter made of polyethylene with a pore width of 0.2 μm in this order. Also, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

[0250]

Table 1

[0251]

Table 2

[0252]

Table 3

[0253] The details of each component described in the table are as follows.

[0254] 〔Resin〕 ·PI Precursor-1 to PI Precursor-3, PBO, Cyclized PI: PI Precursor-1 to PI Precursor-3, PBO, Cyclized PI obtained by the above synthesis examples

[0255] 〔Polymerization inhibitor〕 ·A-1 to A-4: Compounds with the following structures

Chem.

[0256] 〔Migration inhibitor〕 ·B-1 to B-2: Compounds with the following structures

Chem.

[0257] 〔Silane coupling agent〕 ·C-1 to C-2: Compounds with the following structures

Chem.

[0258] 〔Polymerization initiator〕 ·D-1 to D-12: Compounds with the following structures

Chem.

[0259] 〔Polymerizable compound〕 ·E-1: Compounds with the following structures

Chem.

[0260] 〔Thermal base generator〕 ·F-1: Compound with the following structure

[0261] 〔Basic compound〕 ·G-1 to G-2: Compounds with the following structure

Chem.

[0262] 〔Sensitizer〕 ·H-1: Compound with the following structure

Chem.

[0263] 〔Solvent〕 ·S-1: N-Methyl-2-pyrrolidone (NMP) ·S-2: Ethyl lactate (EL) ·S-3: γ-Butyrolactone (GBL) ·S-4: Dimethyl sulfoxide (DMSO) ·S-5: Propylene glycol monomethyl ether acetate (PGMEA)

[0264] <Evaluation> 〔Measurement of viscosity of the composition〕 The viscosity of the resin composition or comparative composition prepared in each example or comparative example was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement results were described in the "Viscosity" column of "Physical Properties" in the table. Note that 1 cp = 1 mPa·s. Also, the measurement temperature was set at 25°C.

[0265] 〔Measurement of water content of the composition〕 The water content of the resin composition or comparative composition prepared in each example or comparative example (the mass of water contained in the total mass of the composition) was measured using a Karl Fischer moisture meter. The measurement results were described in the "Water Content" column of "Physical Properties" in the table.

[0266] 〔Evaluation of stability over time〕 Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity (a) immediately after liquid preparation and the viscosity of the liquid stored for two weeks at the storage temperature described in the table were measured. The viscosity change rate (%) was calculated using the following formula and evaluated according to the following evaluation criteria. Viscosity change rate (%) = absolute value of ((a) - (b)) / (b) × 100 Specifically, in each example or comparative example, the prepared resin composition or comparative composition was filled into the container described in the "Type" column of the "Container" in the table to produce a container body. The i-line transmittance of each container and the h-line transmittance of each container were described in the columns of "i-line transmittance of the container" and "h-line transmittance of the container" in the table, respectively. Also, the porosity of the container at the time of filling was taken as the value described in the column of "Container porosity" in the table. In the example where "A" was described in the "Type" column of the container, as the container, a Clean Barrier (registered trademark) bottle (4L, brown) manufactured by Nissin Cellulose Co., Ltd. was used. A perspective view showing the outline of the Clean Barrier (registered trademark) bottle (storage container) manufactured by Nissin Cellulose Co., Ltd. is shown in FIG. 1. In FIG. 1, the Clean Barrier (registered trademark) bottle (storage container 10) manufactured by Nissin Cellulose Co., Ltd. has an opening 12, and the diameter D of the opening 12 (pouring spout) is 27.8 mm. Although not shown in FIG. 1, the storage container 10 has a handle. Also, the opening 12 can be sealed with a screw cap and was sealed during storage. FIG. 2 is a cross-sectional view showing the outline of the storage container 10. In FIG. 2, the resin composition 14 is filled in the storage container 10. Also, there is a void portion 16 in the storage container 10. The porosity is the value described in "Container porosity" in the table. Also, the wall 18 of the storage container has a thickness of 2 mm. Although omitted in FIG. 2, the wall 18 of the storage container actually has a three-layer structure. An enlarged view of the wall 18 of the storage container is shown in FIG. 3. FIG. 3 is a cross-sectional view showing the outline of the wall 18 of the storage container. In FIG. 3, the wall 18 of the storage container is composed of three layers: an outer layer 20, an intermediate layer 22, and an inner layer 24. Also in FIG. 3, 14 is the resin composition. The outer layer 20 is a resin layer made of high-density polyethylene containing a light-shielding pigment. The intermediate layer 22 is a resin layer made of a gas barrier resin. The inner layer 24 is a resin layer made of an olefin resin (high-density polyethylene). In the example where "B" is described in the "Type" column of the container, as the container, a Clean Barrier (registered trademark) bottle (4L, white) manufactured by Asahi Kasei Corporation was used. The above container contains metal oxide particles in the outer layer. In the example where "C" is described in the "Type" column of the container, as the container, a polyethylene narrow-mouth bottle with a handle manufactured by Takahashi Kasei Co., Ltd., material HDPE (high-density polyethylene), capacity 4000 mL was used. The obtained container was stored for 2 weeks under the conditions of white light at the temperature described in the "Storage Temperature" column of Table 1. From the viscosities of the composition before and after storage, the viscosity change rate was calculated according to the above formula. Using the above viscosity change rate as the index value, evaluation was performed according to the following evaluation criteria. The measurement temperature of the viscosity was set at 25°C. The evaluation results were described in the "Stability over Time" column of the table. It can be said that the smaller the viscosity change rate, the better the stability over time. - Evaluation Criteria - A: The above viscosity change rate (%) was less than 10%. B: The above viscosity change rate (%) was 10% or more and less than 30%. C: The above viscosity change rate (%) was 30% or more and less than 50%. D: The above viscosity change rate (%) was 50% or more.

[0267] 〔Evaluation of Coating Defects〕 In each example or comparative example, a container was manufactured by the same method as the evaluation of the above stability over time. The above container was stored for 2 weeks under the conditions of white light at the temperature described in the "Storage Temperature" column of Table 1. After taking out the resin composition or the comparative composition from the container after storage and returning it to 25°C, it was applied onto an 8-inch Si substrate by the spin coating method (2000 rpm, 30 seconds), and the Si substrate was heated on a hot plate at 100°C for 5 minutes in the atmosphere to obtain a coating film. The above film was evaluated with a defect evaluation apparatus SP1 (KLA Tencor), and the number of defects with a defect diameter of 10 μm or less was used as an index. It can be said that the coating defects are more suppressed as the number of defects is smaller. -Evaluation Criteria- A: The number of the above defects was less than 300. B: The number of the above defects was 300 or more and less than 1000. C: The number of the above defects was 1000 or more and less than 3000. D: The number of the above defects was 3000 or more.

[0268] 〔Evaluation of Resolution〕 In each example or comparative example, a container was manufactured in the same manner as in the evaluation of the above-mentioned stability over time. The above container was stored for 2 weeks under the conditions of the temperature described in the "Storage Temperature" column of Table 1 under white light. After taking out the resin composition or the comparative composition from the container after storage and returning it to 25°C, it was applied onto an 8-inch silicon substrate. In Examples 3 and 4, the slit coating method was used, and in other examples or comparative examples, the spin coating method was used. The silicon substrate was heated on a hot plate at 100°C for 5 minutes in the atmosphere to obtain a coating film. The coating conditions were appropriately set so that the coating film thickness was 10 μm. Next, using a photomask of a fuse box with a step of 1 μm from 5 μm to 25 μm, the coating film was exposed with an i-line stepper (NA = 0.5). The exposure amount was set to the exposure amount that minimized the minimum line width described later. After developing the exposed coating film with cyclopentanone for 60 seconds, it was rinsed with PGMEA (propylene glycol monomethyl ether acetate). In the pattern obtained after development, among the line patterns where the silicon wafer is exposed between the line patterns, the line width of the one with the smallest line width was evaluated according to the following evaluation criteria as the "minimum line width". It can be said that the smaller the line width, the better the resolution. For example, it represents that the metal wiring width formed in the subsequent plating process can be miniaturized, resulting in a preferable result. The measurement limit is 5 μm. The evaluation results are described in the "Resolution" column in the table. -Evaluation Criteria- A: The minimum line width was 5 μm or more and less than 8 μm. B: The minimum line width was 8 μm or more and less than 10 μm. C: The minimum line width was 10 μm or more and less than 12 μm. D: The minimum line width was 12 μm or more.

[0269] 〔Evaluation of Elongation〕 In each example or comparative example, a container was manufactured by the same method as the evaluation of the above-mentioned stability over time. The above container was stored for 3 days under the conditions of white light at the temperature described in the "Storage Temperature" column of Table 1. After returning the resin composition or comparative composition taken out from the stored container to 25 °C, it was applied onto a silicon wafer. For Examples 3 and 4, the slit coating method was used, and for other examples or comparative examples, the spin coating method was used. The above silicon substrate was heated on a hot plate in the atmosphere at 100 °C for 5 minutes to obtain a coating film (composition layer). The coating conditions were appropriately set so that the coating film thickness was 10 μm. The silicon wafer with the obtained composition layer applied thereon was dried on a hot plate at 100 °C for 45 minutes to form a photosensitive resin composition layer with a uniform thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01) with an exposure energy of 400 mJ / cm 2 The exposed composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 5 °C / min until it reached 230 °C and then heated for 3 hours. The cured resin layer was immersed in a 3 mass% hydrofluoric acid solution to peel the resin layer from the silicon wafer and obtain a resin film. A tensile strength test was conducted on the resin film peeled from the silicon wafer. The test was carried out using a tensile testing machine (Tensilon) with a crosshead speed of 300 mm / min, a sample width of 10 mm, and a sample length of 50 mm. The elongation at break was measured in accordance with JIS-K6251 (Japanese Industrial Standard) in the longitudinal and width directions of the film at 25°C and 65% RH (relative humidity). For the evaluation, the elongation at break at the time of cutting was measured 10 times each, and the arithmetic mean value was used as the index value. The results were classified as follows and evaluated according to the evaluation criteria. The evaluation results were described in the "Elongation" column in the table. The larger the above index value, the greater the elongation, indicating excellent mechanical properties. - Evaluation Criteria - A: The above index value was 60% or more. B: The above index value was 55% or more and less than 60%. C: The above index value was 50% or more and less than 55%. D: The above index value was less than 50%.

[0270] From the above results, it can be seen that the storage stability of the resin composition is improved by using the container obtained by the method for manufacturing the container of the present invention. The containers according to Comparative Examples 1 to 3 were not obtained by the method for manufacturing the container of the present invention in terms of the storage temperature and the i-line transmittance and h-line transmittance of the storage container. In such a case, it can be seen that at least the storage stability is inferior.

[0271] <Example 101> A container was manufactured by the same method as the evaluation of the above-mentioned stability over time in Example 1. The above container was stored for 2 weeks under the conditions of the temperature described in the column of "Storage Temperature" in Example 1 and under white light. The resin composition taken out from the container after the above storage was applied in layers on the surface of the copper thin layer of the resin substrate having a copper thin layer formed on the surface by a spin coating method, dried at 100°C for 5 minutes, and after forming a photosensitive film with a film thickness of 20 μm, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10 μm). After the above exposure, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a pattern of the layer. Next, under a nitrogen atmosphere, the temperature was raised at a rate of 10°C / min. After reaching 230°C, it was maintained at 230°C for 180 minutes to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer was excellent in insulation. In addition, when a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that it operated without problems.

Explanation of Reference Numerals

[0272] 10: Storage container, 12: Opening, 14: Resin composition, 16: Void portion, 18: Wall of storage container, 20: Outer layer, 22: Intermediate layer, 24: Inner layer, D: Diameter of opening

Claims

1. A step of filling a storage container with a resin composition containing a resin which is a cyclized resin or a precursor thereof, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator to obtain a container, and a step of storing the container under temperature conditions below 0°C, wherein both the i-line transmittance and the h-line transmittance of the storage container are 1% or less, and the porosity of the container represented by the following formula is 1% by volume or more and 40% by volume or less, A method for manufacturing a container. Porosity (%) = (1 - (volume of the resin composition in the container / capacity of the storage container)) x 100

2. The method for manufacturing a container according to claim 1, wherein the polymerization initiator contains at least one of the compounds represented by any of the following formulas (D-1) to (D-11). 【Chemical 1】

3. The method for manufacturing a container according to claim 1 or 2, wherein the porosity is 1 to 30% by volume.

4. The method for manufacturing a container according to any one of claims 1 to 3, wherein the porosity is 1 to 20% by volume.

5. The method for manufacturing a container according to any one of claims 1 to 4, wherein the porosity is 1 to 15% by volume.

6. The method for manufacturing a container according to any one of claims 1 to 5, wherein the porosity is 5 to 15% by volume.

7. The method for manufacturing a container according to any one of claims 1 to 6, wherein both the i-line transmittance and the h-line transmittance of the storage container are 0.1% or less.

8. The method for manufacturing a container according to any one of claims 1 to 7, wherein both the i-line transmittance and the h-line transmittance of the storage container are 0.01% or less.

9. The method for manufacturing a container according to any one of claims 1 to 8, wherein the wall of the storage container has two or more resin layers.

10. The method for manufacturing a container according to any one of claims 1 to 9, wherein the resin composition contains at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and ethyl lactate as a solvent.

11. The method for manufacturing a container according to any one of claims 1 to 10, wherein the viscosity of the resin composition at 25°C is 50 to 5000 cp.

12. The method for manufacturing a container according to any one of claims 1 to 11, wherein the water content in the total mass of the resin composition is 1.0% by mass or less.

13. The method for producing a container according to any one of claims 1 to 12, wherein the resin composition contains a component having a polymerizable group.

14. The method for producing a container according to any one of claims 1 to 13, wherein the resin composition contains a sensitizer.

15. A storage method for storing a resin composition containing a resin that is a cyclized resin or a precursor thereof, and at least one polymerization initiator selected from the group consisting of an oxime-based polymerization initiator and a metallocene-based polymerization initiator in a storage container, wherein both the i-line transmittance and the h-line transmittance of the storage container are 1% or less, wherein the storage is performed under a temperature condition of less than 0°C, wherein the porosity of the resin composition in the storage container during storage is 1% by volume or more and 40% by volume or less as represented by the following formula, A method for storing a resin composition. Porosity (%) = (1 - (volume of the resin composition in the storage container / capacity of the storage container)) x 100

16. The method for storing a resin composition according to claim 15, wherein the polymerization initiator contains at least one of the compounds represented by any one of the following formulas (D-1) to (D-11). 【Chemical 2】

17. The method for storing a resin composition according to claim 15 or 16, wherein the porosity is 1 to 30% by volume.

18. The method for storing a resin composition according to any one of claims 15 to 17, wherein the porosity is 1 to 15%, and the viscosity of the resin composition at 25°C is 50 to 5000 cp.

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