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

Abstract

Provided are a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device, the resin composition containing at least one resin selected from the group consisting of polyimides and precursors thereof, the dielectric loss tangent of a cured product obtained by heating the resin composition at 230 DEG C for 1 hour is less than 0.03.

Description

Technical Field

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

[0002] Nowadays, technologies for producing resin materials from resin compositions containing resins are being utilized in various fields.

[0003] For example, polyimide is used in a variety of applications due to its excellent heat resistance and insulation properties. These applications are not particularly limited, but, for example, in the case of semiconductor devices for mounting, examples include use as insulating films, sealing materials, and protective films. Furthermore, it can also be used as base films and cover films for flexible substrates.

[0004] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing polyimide or a polyimide precursor.

[0005] For example, such a resin composition is applied to a substrate by coating to form a photosensitive film, and then subjected to exposure, development, heating, etc. as needed to form a cured product on the substrate.

[0006] The polyimide precursor is cyclized by, for example, heating and becomes a polyimide in a cured product.

[0007] The resin composition can be applied using known coating methods, and therefore offers excellent manufacturing adaptability, such as a high degree of design freedom in terms of the shape, size, and application location of the resin composition. Given the excellent manufacturing adaptability in addition to the high performance of polyimide, the expansion of industrial applications of the resin composition is increasingly anticipated.

[0008] For example, Patent Document 1 describes a curable resin composition comprising: at least one resin having a polyalkyleneoxy group and a polymerizable group and selected from polyimide and polyimide precursors; a polymerization initiator; a polymerizable compound; and a solvent.

[0009] Patent Document 2 describes a curable resin composition containing a resin having a specific repeating unit and a solvent.

[0010] Previous technical literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2020 / 255859

[0013] Patent Document 2: International Publication No. 2021 / 039782 Summary of the Invention

[0014] Technical issues to be solved by the invention

[0015] When a cured product is obtained from a resin composition containing at least one resin selected from polyimide and a polyimide precursor, the cured product may be formed by applying the resin composition to a substrate having a multilayered step structure, such as a substrate having metal wiring formed thereon.

[0016] However, when a cured product is formed on a substrate having such a step structure, the surface of the cured product is required to be flat.

[0017] In this specification, a resin composition that easily forms a cured product having a flat surface is also referred to as a resin composition in which the obtained cured product has excellent flatness.

[0018] Furthermore, a method for producing a cured product that easily forms a cured product having a flat surface is also described as a method for producing a cured product in which the obtained cured product has excellent flatness.

[0019] An object of the present invention is to provide a resin composition having excellent flatness of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, a method for manufacturing the above laminate, a method for manufacturing a semiconductor device including the method for manufacturing the above cured product, and a semiconductor device containing the above cured product.

[0020] Another object of the present invention is to provide a method for producing a cured product having excellent flatness.

[0021] Means for solving technical problems

[0022] Hereinafter, examples of representative embodiments of the present invention will be described.

[0023] <1> A resin composition comprising at least one resin selected from polyimide and its precursor,

[0024] The dielectric loss tangent of a cured product obtained by heating the resin composition at 230° C. for 1 hour is less than 0.03.

[0025] <2> A resin composition comprising at least one resin selected from polyimide and its precursor,

[0026] The dielectric loss tangent of the resin is less than 0.025.

[0027] <3> according to <1> or <2> The resin composition further contains a polymerizable compound and a photopolymerization initiator.

[0028] <4> according to <3> The resin composition, wherein

[0029] The polymerizable compound contains an acryloyl group.

[0030] <5> according to <1> to <4> The resin composition according to any one of claims , wherein

[0031] The weight average molecular weight of the above resin is 20,000 or less.

[0032] <6> according to <1> to <5> The resin composition according to any one of the preceding claims, wherein

[0033] The above resin has a polymerizable group.

[0034] <7> according to <1> to <6> The resin composition according to any one of claims , wherein

[0035] The above resin has a vinylphenyl group.

[0036] <8> according to <1> to <7> The resin composition according to any one of claims , wherein

[0037] The resin has a group obtained by removing two or more hydrogen atoms from a structure represented by the following formula (A-1).

[0038] [Chemical Formula 1]

[0039]

[0040] In formula (A-1), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

[0041] <9> according to <1> to <8> The resin composition according to any one of claims , further comprising a solvent having a boiling point of 180° C. or lower.

[0042] <10> according to <9> The resin composition further contains a solvent with a boiling point exceeding 180°C.

[0043] <11> according to <1> to <10> The resin composition according to any one of claims 1 to 4, further comprising a surfactant.

[0044] <12> according to <11> The resin composition, wherein

[0045] The above-mentioned surfactant is a compound containing a silicon atom.

[0046] <13> according to <1> to <12> The curable resin composition according to any one of claims 1 to 5, which is used for forming an interlayer insulating film for a redistribution layer.

[0047] <14> A solidified material, which is solidified <1> to <13> Made from the resin composition described in any one of the above.

[0048] <15> A laminate comprising two or more layers of <14> The layer composed of the cured product includes a metal layer between any of the layers composed of the cured product.

[0049] <16> A method for producing a solidified product, comprising: <1> to <13> The resin composition described in any one of the above is suitable for a film forming step of forming a film on a substrate.

[0050] <17> A method for producing a solidified material, comprising:

[0051] A drying step of heating and drying a resin composition containing at least one resin selected from polyimide and its precursor, wherein the resin has a dielectric loss tangent of less than 0.25, to form a film;

[0052] a heating step of heating the film,

[0053] The method for producing the cured product satisfies any one of the following conditions i to v,

[0054] Condition i: The heating temperature in the drying step is 120°C or higher and lower than 150°C.

[0055] Condition ii: The heating temperature in the drying step is lower than 120° C. and the heating time is 5 minutes or longer.

[0056] Condition iii: The heating temperature in the heating step is 240° C. or higher.

[0057] Condition iv: The heating temperature in the heating step is 150° C. or higher and lower than 240° C., and the heating time is 3 hours or longer.

[0058] Condition v: The heating process includes at least a first heating process and a second heating process performed after the first heating process, the heating temperature in the first heating process is 150° C. or higher and lower than 200° C., and the heating temperature in the second heating process is 200° C. or higher.

[0059] <18> A method for producing a solidified material, comprising:

[0060] a drying step of heating and drying a curable composition containing at least one resin selected from polyimide and its precursor to form a film;

[0061] a heating step of heating the film,

[0062] The dielectric loss tangent of the obtained cured product is less than 0.03.

[0063] The method for producing the cured product satisfies any one of the following conditions i to v,

[0064] Condition i: The heating temperature in the drying step is 120°C or higher and lower than 150°C.

[0065] Condition ii: The heating temperature in the drying step is lower than 120° C. and the heating time is 5 minutes or longer.

[0066] Condition iii: The heating temperature in the heating step is 240° C. or higher.

[0067] Condition iv: The heating temperature in the heating step is 150° C. or higher and lower than 240° C., and the heating time is 3 hours or longer.

[0068] Condition v: The heating process includes at least a first heating process and a second heating process performed after the first heating process, the heating temperature in the first heating process is 150° C. or higher and lower than 200° C., and the heating temperature in the second heating process is 200° C. or higher.

[0069] <19> like <17> or <18> The method for producing a solidified material, wherein:

[0070] Between the drying step and the heating step, an exposure step of selectively exposing the film to light and a development step of developing the film using a developer to form a pattern are included.

[0071] <20> A method for manufacturing a laminated body, comprising: <16> The manufacturing method of the solidified material.

[0072] <21> A method for manufacturing a semiconductor device, comprising: <16> The manufacturing method of the solidified material.

[0073] <22> A semiconductor device comprising <14> The solidified material.

[0074] Effects of the Invention

[0075] According to the present invention, there can be provided a resin composition having excellent flatness of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, a method for manufacturing the above laminate, a method for manufacturing a semiconductor device including the method for manufacturing the above cured product, and a semiconductor device containing the above cured product.

[0076] Furthermore, according to the present invention, a method for producing a cured product having excellent flatness can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 This is a schematic cross-sectional view showing a state where a solidified material is formed on a silicon wafer having copper wiring formed thereon during flatness evaluation.

[0078] Figure 2 This is a schematic plan view showing the measurement position of the film thickness of a dry film formed on a circular silicon wafer in the evaluation of coating uniformity within the wafer surface. DETAILED DESCRIPTION

[0079] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0080] In this specification, the numerical range expressed by the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0081] In this specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0082] In the description of groups (atomic groups), the term "unsubstituted" or "unsubstituted" includes groups (atomic groups) without substitution as well as groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0083] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0084] In this specification, “(meth)acrylate” means both or either of “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either of “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0085] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0086] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, the solid content concentration in this specification refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0087] In this specification, as long as there is no special explanation, weight average molecular weight (Mw) and number average molecular weight (Mn) are the values ​​measured by gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, using HLC-8220GPC (TOSOH CORPORATION system), protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as column, thus weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights are measured using NMP (N- methyl -2- pyrrolidone) as eluent. Furthermore, as long as there is no special explanation, the detection in GPC determination uses a UV ray (ultraviolet) detector with a wavelength of 254nm.

[0088] In this specification, about the positional relationship of each layer constituting laminated body, when being recorded as " on " or " down ", as long as there are other layers on the upper side or lower side of the layer becoming a benchmark in the multiple layers concerned. That is, the 3rd layer or the 3rd element can be further sandwiched between the layer becoming a benchmark and the above-mentioned other layers, and the layer becoming a benchmark and the above-mentioned other layers do not need to contact. Unless otherwise specified, the direction of the substrate stacked layer will be referred to as " on ", or, when there is a resin composition layer, the direction from the substrate toward the resin composition layer will be referred to as " on ", and its opposite direction will be referred to as " down ". In addition, the setting of these up and down directions is for the convenience in this specification, and in actual mode, the " up " direction in this specification can also be different from the vertical direction.

[0089] In this specification, unless otherwise specified, each component contained in a composition may include two or more compounds belonging to the component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to the component.

[0090] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0091] In this specification, a combination of preferred embodiments is considered a more preferred embodiment.

[0092] (Resin composition)

[0093] The first embodiment of the resin composition of the present invention (hereinafter also referred to as the "first resin composition") contains at least one resin selected from polyimide and its precursor, and the dielectric loss tangent of a cured product obtained by heating the resin composition at 230°C for 1 hour is less than 0.03.

[0094] The resin composition of the second embodiment of the present invention (hereinafter also simply referred to as the "second resin composition") contains at least one resin selected from polyimide and its precursor, and the dielectric loss tangent of the resin is less than 0.025.

[0095] Hereinafter, the first resin composition and the second resin composition are also simply referred to as "resin compositions".

[0096] Hereinafter, at least one resin selected from polyimide and a precursor thereof contained in the first resin composition is also referred to as a "first specific resin."

[0097] Hereinafter, the at least one resin selected from polyimide and its precursor contained in the second resin composition and having a dielectric loss tangent of less than 0.025 is also referred to as a “second specific resin”.

[0098] Hereinafter, when simply described as "specific resin", it refers to both the first specific resin and the second specific resin.

[0099] The resin composition of the present invention is preferably used to form a photosensitive film (subject to exposure and development), and is preferably used to form a film (subject to exposure and development using a developer containing an organic solvent).

[0100] The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, and the like, and is preferably used to form an interlayer insulating film for a redistribution layer.

[0101] In particular, it is one of the preferred embodiments of the present invention that the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer.

[0102] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development.

[0103] In the present invention, in exposure and development, negative-tone development refers to development in which unexposed areas are removed by development, and positive-tone development refers to development in which exposed areas are removed by development.

[0104] As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and the development method described in the development step in the description of the method for producing a cured product described later can be used.

[0105] According to the resin composition of the present invention, a cured product having a low dielectric constant can be obtained.

[0106] The mechanism by which the above-mentioned effects are obtained is not yet clear, but is presumed to be as follows.

[0107] As described above, in the method of applying a resin composition to a substrate having a step structure and then heating or the like to obtain a cured product, the obtained cured product may have poor flatness.

[0108] As a result of intensive studies conducted by the present inventors, it was found that the deterioration of the flatness is caused by shrinkage of the film during heating.

[0109] Specifically, it was found that the shrinkage amount is greater in thick film portions such as portions where wiring is formed or portions where wiring is not formed than in thin film portions, and thus the portions where wiring is not formed in the cured product may be recessed.

[0110] The cured product of the first embodiment of the present invention has a dielectric loss tangent of less than 0.03.

[0111] In such a cured product, it is considered that the imide ring content is low and the stacking properties between polymers are reduced, so the reflow property is improved and the flatness is excellent.

[0112] Furthermore, the dielectric loss tangent of the resin of the second embodiment of the present invention is less than 0.025. This is believed to be because the resin has a low (cyclized) imide ring content and reduced stacking properties between polymers, thereby improving reflow properties and achieving excellent flatness.

[0113] In the present invention, the reflow property refers to a property in which the unevenness is evened out by softening and flowing the film by heating or the like.

[0114] In particular, in the first and second aspects, when polyimide is used, less (eg, ester portion in the polyimide precursor) is released from the resin, and shrinkage of the film associated with the effect can be suppressed, thus facilitating improvement in flatness.

[0115] However, neither Patent Documents 1 nor 2 describes a method in which the dielectric loss tangent of the cured product is less than 0.03, nor a method in which the dielectric loss tangent of the resin is less than 0.025.

[0116] Hereinafter, the physical properties of the resin composition of the present invention and the components contained in the resin composition of the present invention will be described in detail.

[0117] <Dielectric loss tangent>

[0118] The dielectric loss tangent (hereinafter also referred to as tan δ) of the cured product obtained by heating the first resin composition at 230° C. for 1 hour is less than 0.03, preferably less than 0.025, more preferably less than 0.020, and further preferably less than 0.015.

[0119] The lower limit of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or greater, for example.

[0120] The dielectric loss tangent of a cured product obtained by heating the second resin composition at 230° C. for 1 hour is preferably less than 0.03, more preferably less than 0.025, further preferably less than 0.020, and particularly preferably less than 0.015.

[0121] The lower limit of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or greater, for example.

[0122] The details of the method for measuring tan δ of the cured product can be carried out by the method described in the examples below.

[0123] <Specific resin>

[0124] The first resin composition contains at least one resin (first specific resin) selected from polyimide and a precursor thereof.

[0125] The second resin composition contains at least one resin selected from polyimide and a precursor thereof, and has a dielectric loss tangent of less than 0.025 (second specific resin).

[0126] The dielectric loss tangent of the first specific resin is preferably less than 0.025, more preferably less than 0.020, further preferably less than 0.015, and particularly preferably less than 0.010.

[0127] The lower limit of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or greater, for example.

[0128] The dielectric loss tangent of the second specific resin is less than 0.025, preferably less than 0.020, more preferably less than 0.015, and further preferably less than 0.010.

[0129] The lower limit of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or greater, for example.

[0130] The details of the method for measuring tan δ of the above-mentioned specific resin can be carried out by the method described in the examples below.

[0131] Furthermore, for example, when a plurality of resins are included as the first specific resin, it suffices that the dielectric loss tangent of at least one of the resins is within the above-mentioned range. Furthermore, it is also a preferred embodiment of the present invention that the dielectric loss tangent of all of the plurality of resins is within the above-mentioned range.

[0132] The content of the resin having a dielectric loss tangent within the above range relative to the total mass of the first specific resin is preferably 50% by mass or greater, more preferably 60% by mass or greater, and even more preferably 70% by mass or greater. The upper limit of the above content is not particularly limited, and an embodiment of 100% by mass is also a preferred embodiment of the present invention.

[0133] The resin composition of the present invention preferably contains polyimide as the specific resin.

[0134] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0135] When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably contains a free radical polymerization initiator, more preferably a free radical polymerization initiator and a free radical crosslinking agent. Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition.

[0136] Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As the radical polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.

[0137] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. Preferred are groups having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group, and more preferred is a vinylphenyl group.

[0138] The polymerizable group value in the specific resin (the total molar amount of the polymerizable groups per 1 g of the specific resin) is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0139] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0140] When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed from such a resin composition.

[0141] The specific resin preferably has a group formed by removing two or more hydrogen atoms from a structure represented by the following formula (A-1), and more preferably has a group formed by removing two or more hydrogen atoms from a structure represented by the following formula (A-2).

[0142] [Chemical Formula 2]

[0143]

[0144] In formula (A-1), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

[0145] A 1 ~A 3 Preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group consisting of a combination of two or more of these. More preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, or a group consisting of a combination of two or more of these. Still more preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms or -O-.

[0146] In particular, A is preferred 1 and A 3 It is -O-.

[0147] In particular, A is preferred 2 It is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.

[0148] Among these, A 1 and A 3 is -0- and A 2 The embodiment of -C(CH3)2- is also one of the preferred embodiments of the present invention.

[0149] The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4.

[0150] Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH2-, -C(CH3)2-, and -C(CF3)2-, among which -C(CH3)2- is preferred.

[0151] Examples of the substituents on the four benzene rings described in formula (A-1) include fluorine atoms and hydrocarbon groups having 1 to 10 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms.

[0152] Furthermore, an embodiment in which all four benzene rings described in formula (A-1) are unsubstituted is also one of the preferred embodiments of the present invention.

[0153] Furthermore, the specific resin preferably contains a structure represented by formula (A-1) as R in formula (2) described later. 115 or R 111 These methods will be described later.

[0154] Specific examples of the structure represented by formula (A-1) are described below, but the present invention is not limited to these.

[0155] [Chemical Formula 3]

[0156]

[0157] Furthermore, an embodiment in which the weight average molecular weight of the specific resin is 20,000 or less is also one of the preferred embodiments of the present invention.

[0158] By adopting this configuration, reflow during the heating step is easily induced, resulting in excellent flatness. Furthermore, the resin composition has excellent solubility in a developer, and therefore, it is considered that the obtained cured product has excellent resolution.

[0159] Furthermore, the weight average molecular weight is preferably 17,000 or less, more preferably 13,000 or less, and even more preferably 10,000 or less.

[0160] The lower limit of the weight average molecular weight is not particularly limited, but is preferably 5,000 or more.

[0161] 〔Polyimide precursor〕

[0162] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2).

[0163] [Chemical Formula 4]

[0164]

[0165] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0166] A in formula (2) 1and A 2 Each independently represents an oxygen atom or -NR Z -, preferably an oxygen atom.

[0167] R in formula (2) 111 Represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, preferably an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group in the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, preferably -Ar-L-Ar-. Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of a combination of two or more of the foregoing. The preferred ranges are as described above.

[0168] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic, or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0169] Specifically, R 111 Preferred are diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably diamines containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon groups in the linear or branched aliphatic groups may be substituted with groups containing heteroatoms, and the hydrocarbon groups in the ring members of the cyclic aliphatic and aromatic groups may be substituted with groups containing heteroatoms. Examples of groups containing aromatic groups include the following.

[0170] [Chemical Formula 5]

[0171]

[0172] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0173] Where * indicates the bonding position with other structures.

[0174] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane.

[0175] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine;

[0176] m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

[0177] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0178] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0179] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group herein is preferably an alkylene group.

[0180] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0181] Formula (51)

[0182] [Chemical Formula 6]

[0183]

[0184] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to the nitrogen atom in formula (2).

[0185] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0186] [Chemical Formula 7]

[0187]

[0188] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to the nitrogen atom in formula (2).

[0189] Examples of the diamine that imparts the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

[0190] Furthermore, R is also preferred. 111 is a group represented by the following formula (71). In the above embodiment, it is preferred that R 111 It is a group represented by the following formula (72).

[0191] Formula (71) is a group formed by removing two hydrogen atoms from the structure represented by the above formula (A-1), and formula (72) is a group formed by removing two hydrogen atoms from the structure represented by the above formula (A-2).

[0192] [Chemical Formula 8]

[0193]

[0194] In formula (71), A 1 ~A 3Each independently represents a single bond or a divalent linking group, * represents the bonding position to the nitrogen atom in formula (2), and the four benzene rings described in formula (71) may each have a substituent.

[0195] In formula (72), * represents the bonding position to the nitrogen atom in formula (2).

[0196] In formula (71), A 1 ~A 3 , and the preferred embodiment of the substituent in the benzene ring is the same as that of A in the above formula (A-1). 1 ~A 3 , and the preferred embodiments of the substituents in the benzene ring are the same.

[0197] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[0198] In formula (5) or formula (6), * each independently represents a bonding position to another structure.

[0199] [Chemical Formula 9]

[0200]

[0201] In formula (5), R 112 It is a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination thereof, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C0-, -S- and -SO2-, further preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0202] Furthermore, R is also preferred. 115 is a group represented by the following formula (7). In the above embodiment, it is preferred that R 111 It is a group represented by the following formula (7-2).

[0203] Formula (7) is a group formed by removing four hydrogen atoms from the structure represented by the above formula (A-1), and formula (7-2) is a group formed by removing four hydrogen atoms from the structure represented by the above formula (A-2).

[0204] [Chemical Formula 10]

[0205]

[0206] In formula (7), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, * represents the bonding position to the carbonyl group in formula (2), and the four benzene rings described in formula (7) may each have a substituent.

[0207] In this specification, a bond that crosses the side of a ring structure means a bond that replaces any of the hydrogen atoms in the ring structure.

[0208] In formula (7-2), * represents a bonding position to the carbonyl group in formula (2).

[0209] In formula (7), A 1 ~A 3 , and the preferred embodiment of the substituent in the benzene ring is the same as that of A in the above formula (A-1). 1 ~A 3 , and the preferred embodiments of the substituents in the benzene ring are the same.

[0210] Specifically, R 115 Examples include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. 115 The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues.

[0211] Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0212] [Chemical Formula 11]

[0213]

[0214] In formula (O), R 115 Represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The meanings are the same and the preferred ranges are also the same.

[0215] Specific examples of tetracarboxylic dianhydrides include pyromellitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

[0216] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned as preferred examples.

[0217] In formula (2), R 111 and R 114 At least one of R may also have an OH group. More specifically, 111 , for example, residues of bisaminophenol derivatives.

[0218] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. In addition, it is preferred that R 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114At least one of the polyimide precursors contains more than two polymerizable groups. As a polymerizable group, it is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0219] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferred groups include a group represented by the following formula (III).

[0220] [Chemical Formula 12]

[0221]

[0222] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and preferably a hydrogen atom or a methyl group.

[0223] In formula (III), * represents a bonding position with other structures.

[0224] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(0H)CH2-, a cycloalkylene group, or a polyalkyleneoxy group.

[0225] Preferred R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. Alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are further preferred.

[0226] In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0227] When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an alternating arrangement.

[0228] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0229] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0230] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0231] From the perspective of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups. A polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0232] In formula (2), when R 113 When it is a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a salt pair with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0233] In formula (2), R 113 and R 114 At least one of the groups may be a polarity conversion 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 produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Preferred groups include acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups. From the perspective of exposure sensitivity, acetal groups and ketal groups are more preferred.

[0234] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl and tetrahydrofuranyl are preferred.

[0235] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0236] Furthermore, in order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0237] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), the exposure latitude can be further increased.

[0238] Formula (2-A)

[0239] [Chemical Formula 13]

[0240]

[0241] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0242] A 1 、A 2 、R 111 、R 113 and R 114 The meanings of are independently the same as those of A in formula (2) 1 、A 2 、R 111 、R 113 and R 114 The meanings and preferred ranges are the same.

[0243] R 112 The meaning of is the same as R in formula (5) 112 The meanings and preferred ranges are the same.

[0244] Furthermore, it is preferred that the polyimide precursor contains a repeating unit represented by formula (1-2) as the repeating unit represented by formula (2).

[0245] [Chemical Formula 14]

[0246]

[0247] In formula (1-2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, X 1 represents an organic group with 4 or more carbon atoms, Y 1 represents an organic group with more than 4 carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R Z represents a hydrogen atom or a monovalent organic group, m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0248] [Chemical Formula 15]

[0249]

[0250] In formula (R-1), L 1 Represents a2+1 valence connecting group, A 1 represents a polymerizable group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-2). 1 or Y 1 bonding position.

[0251] X in formula (1-2) 1 、Y 1 、R 1 The preferred embodiments of n and m are the same as those of X in the formula (1-1) described later. 1 、Y 1 、R 1 , n and m are preferably the same.

[0252] A in formula (1-2) 1 、A 2 、R 113 and R 114 The preferred embodiment is the same as A in the above formula (2) 1 、A 2 、R 113 and R 114 The preferred method is the same.

[0253] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units represented by formula (2), the polyimide precursor may also contain other types of repeating units.

[0254] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) can be 50 mol% or more of the total repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal can be repeating units represented by formula (2).

[0255] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, and even more preferably 7,000 to 20,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 20,000, and even more preferably 4,000 to 10,000.

[0256] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0257] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0258] When the resin composition contains multiple polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor be within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polyimide precursors, calculated as a single resin, be within the above ranges.

[0259] 〔Polyimide〕

[0260] 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.

[0261] In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the perspective of pattern formation, the polyimide preferably dissolves 0.5 g or more, and more preferably dissolves 1.0 g or more. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less.

[0262] From the viewpoint of film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0263] -Fluorine atom-

[0264] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has fluorine atoms.

[0265] For example, the fluorine atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described later 131 Among them, R is more preferably included as a fluorinated alkyl group in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by the formula (4) described later 131 middle.

[0266] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and preferably 20% by mass or less.

[0267] -Silicon atoms-

[0268] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has a silicon atom.

[0269] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 Among them, R is more preferably included in the repeating unit represented by the formula (4) described later as an organo-modified (poly)siloxane structure described later. 131 middle.

[0270] The silicon atom or the organo-modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

[0271] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0272] -Ethylenically unsaturated bond-

[0273] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0274] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0275] The ethylenically unsaturated bond is preferably radically polymerizable.

[0276] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 Among them, it is more preferable that the group having an ethylenically unsaturated bond is contained in R 132 or R 131 middle.

[0277] Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 Among them, it is more preferable that the group having an ethylenically unsaturated bond is contained in R 131 middle.

[0278] Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0279] [Chemical Formula 16]

[0280]

[0281] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0282] In formula (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=0)0-, -0(C=0)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, and the number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group formed by combining two or more of these.

[0283] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof.

[0284] The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0285] Among these, R 21The group is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

[0286] [Chemical Formula 17]

[0287]

[0288] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding position to other structures, and ● represents the bonding position to R in formula (IV). 21 The bonding position of the bonded oxygen atom.

[0289] In formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as that of R in formula (IV). 21 The preferred embodiment is the same as that of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.

[0290] In formula (R1), X is preferably an oxygen atom.

[0291] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

[0292] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).

[0293] The structure represented by formula (R2) can be obtained by, for example, reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0294] The structure represented by formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0295] In formula (IV), * represents a bonding position to another structure, and is preferably a bonding position to the main chain of the polyimide.

[0296] The amount of the ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, relative to the total mass of the polyimide.

[0297] -Polymerizable groups other than groups having an ethylenically unsaturated bond-

[0298] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0299] Examples of polymerizable groups other than the group having an ethylenically unsaturated bond include epoxy groups, cyclic ether groups such as oxetane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups.

[0300] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R131 in the repeating unit represented by the formula (4) described later.

[0301] The amount of the polymerizable groups other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0302] -Polarity conversion group-

[0303] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described in are the same as those in , and preferred embodiments are also the same.

[0304] The polarity conversion group is included in, for example, R in the repeating unit represented by the formula (4) described below. 131 、R 132 , the end of polyimide, etc.

[0305] -Acid value-

[0306] When the polyimide is used for alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more, from the viewpoint of improving developability.

[0307] The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0308] When the polyimide is used for development using a developer containing an organic solvent as the main component (eg, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0309] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0310] As the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferably an acid group, and an acid group having a pKa of 3 to 8 is more preferably an acid group, from the viewpoint of achieving both storage stability and developability.

[0311] The pKa is a value representing the equilibrium constant, Ka, by its negative common logarithm, pKa, taking into account the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is a value calculated based on ACD / ChemSketch (registered trademark). For pKa, reference can be made to the values ​​listed in "Chemical Handbook, 5th Edition, Revised Basics," edited by the Chemical Society of Japan.

[0312] When the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0313] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0314] -phenolic hydroxyl group-

[0315] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0316] The polyimide may have a phenolic hydroxyl group at a main chain terminal or in a side chain.

[0317] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 middle.

[0318] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, relative to the total mass of the polyimide.

[0319] 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).

[0320] [Chemical Formula 18]

[0321]

[0322] In formula (4), R 131 represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0323] Among them, the repeating unit represented by formula (4) may have one of the imide structures open, as in the structure represented by formula (4-A) below. In the structure represented by formula (4-A), the left side of the two imide rings is open, but the right side may also be open. Similarly, in formulas (4-1), (4-2), and (1-1), one of the imide structures may be open.

[0324] [Chemical Formula 19]

[0325]

[0326] In formula (4-A), R 131 Represents a divalent organic group, R 132 Represents a 4-valent organic group, A 1 Represents an oxygen atom or -NR z -, R 114 represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0327] In formula (4-A), R 131 and R 132 The preferred embodiment is the same as R in formula (4) 131 and R 132 The preferred method is the same.

[0328] In formula (4-A), A 1 and R 114 The preferred embodiment is the same as A in formula (2) 1 and R 114 The preferred method is the same.

[0329] In the case of having a polymerizable group, the polymerizable group may be located at R 131 and R 132 At least one of them may be located at a terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0330] Formula (4-1)

[0331] [Chemical Formula 20]

[0332]

[0333] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0334] Formula (4-2)

[0335] [Chemical Formula 21]

[0336]

[0337] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

[0338] Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond and a crosslinkable group other than a group having the above-mentioned ethylenically unsaturated bond.

[0339] R 131 The divalent organic group includes the following: 111 The preferred ranges are the same.

[0340] As R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 example.

[0341] From the perspective of more effectively suppressing warpage during calcination, R 131 A diamine residue having at least two alkylene glycol units in the main chain is preferred. A diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in one molecule is more preferred. A diamine residue containing no aromatic ring is further preferred.

[0342] Examples of diamines containing two or more ethylene glycol chains or propylene glycol chains or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0343] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include the following: 115 The preferred ranges are the same.

[0344] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in formula (4) to form a condensed ring.

[0345] R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0346] It is also preferred that R 131 and R 132 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, and the above (DA-1) to (DA-18) can be mentioned as preferred examples, and as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0347] Furthermore, the polyimide preferably contains a repeating unit represented by the following formula (1-1) as the repeating unit represented by the formula (4).

[0348] [Chemical Formula 22]

[0349]

[0350] In formula (1-1), X 1 represents an organic group with 4 or more carbon atoms, Y 1 represents an organic group with more than 4 carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0351] [Chemical Formula 23]

[0352]

[0353] In formula (R-1), L 1 Represents a2+1 valence connecting group, A 1 represents a polymerizable group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-1). 1 or Y 1 bonding position.

[0354] -R 1 -

[0355] R 1 Each independently represents the structure represented by formula (R-1).

[0356] In formula (R-1), L 1 It represents a2+1 valent linking group.

[0357] L 1 Preferred is a group represented by the following formula (L-1).

[0358] [Chemical Formula 24]

[0359]

[0360] In formula (L-1), L x represents an a2+1 valence linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-1). 1 or Y 1 The bonding position of Z in formula (R-1) is represented by #. 1 bonding position.

[0361] L x An alkylene group 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 further preferred.

[0362] Preferred aspects of a2 in formula (L-1) are the same as preferred aspects of a2 in formula (R-1).

[0363] -A 1 -

[0364] A in formula (R-1) 1 represents a polymerizable group, and preferred embodiments of the polymerizable group are the same as those of the polymerizable group in the above-mentioned specific resin.

[0365] Among them, A in formula (R-1) contained in formula (1-1) 1 At least one of them is preferably a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, and more preferably a vinylphenyl group.

[0366] -a2-

[0367] In formula (R-1), a2 represents an integer of 1 or greater, preferably 1 or 2, and more preferably 1.

[0368] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0369] -X 1 -

[0370] In formula (1-1), X 1It preferably contains a structure in which two or more hydrogen atoms are removed from a structure represented by any one of the following formulae (V-1) to (V-4).

[0371] [Chemical Formula 25]

[0372]

[0373] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0374] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2 With R X3 They can be bonded to form a ring structure.

[0375] In formula (V-2), R X1 Each of the groups is preferably independently an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one of the hydrogen atoms of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0376] In formula (V-3), R X2 and R X3 Preferably, they are each independently a hydrogen atom.

[0377] In R 1 With R 2 When the ring structure is formed by bonding, R X2 With R X3 The structure formed by the bond is preferably a single bond, -O- or -CR2-, more preferably -O- or -CR2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0378] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 1 The bonding positions of the four bonded carbonyl groups, n1 represents an integer of 0 to 5, preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms be substituted by R in the formula (1-1). 1 replace.

[0379] [Chemical Formula 26]

[0380]

[0381] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), X 1 The group represented by the following formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. X1 represents a single bond or -O-, * represents the X in formula (1-1) 1 The bonding positions of the four carbonyl groups bonded. X1 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by well-known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0382] [Chemical Formula 27]

[0383]

[0384] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1 The group represented by the following formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-3-2) is preferred. In the following formula, * represents X in formula (1-1). 1 The bonding positions of the four carbonyl groups bonded. X2 and R X3 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by well-known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (1-1) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (1-1). 1 replace.

[0385] [Chemical Formula 28]

[0386]

[0387] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 1Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents the same group as X in formula (1-1). 1 The bonding positions of the four bonded carbonyl groups, n1 represents an integer from 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (1-1) is an integer from 1 to 4, it is preferred that m hydrogen atoms be substituted by R in the formula (1-1). 1 replace.

[0388] [Chemical Formula 29]

[0389]

[0390] In addition, X 1 It can be R in the above formula (4) 132 The group represented by is obtained by removing m hydrogen atoms.

[0391] And, X 1 It is preferred that the structure does not contain an imide structure.

[0392] In the present invention, the imide structure is a structure represented by -C(=O)N(-*)C(=O)-. * represents a bonding position to another structure.

[0393] Furthermore, X1 preferably does not contain a urethane bond, a urea bond, or an amide bond in its structure.

[0394] In the present invention, the urethane bond refers to the bond consisting of *-OC(=0)-NR N -* indicates a key, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N It is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0395] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom. N The preferred embodiment is as described above.

[0396] In the present invention, the amide bond is *-NR N -C(=O)-* represents a bond, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N The preferred embodiment is as described above.

[0397] In addition, X 1It is preferred that no ester bond be present in the structure.

[0398] In the present invention, the ester bond is a bond represented by *-0-C(=0)-*.

[0399] Among these, X 1 It is preferable that the polyol contains no imide structure, urethane bond, urea bond, or amide bond, and it is preferable that the polyol contains no imide structure, urethane bond, urea bond, amide bond, or ester bond.

[0400] -Y 1 -

[0401] In formula (1-1), Y 1 It preferably contains a structure in which two or more hydrogen atoms are removed from the structure represented by any one of the above formulae (V-1) to (V-4).

[0402] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 1 It is preferably a group formed by removing n hydrogen atoms from a group represented by the following formula (V-1-2). In the following formula, * represents Y in formula (1-1). 1 The bonding position of the two nitrogen atoms bonded, n1 represents an integer of 1 to 5. The number n of hydrogen atoms in the following structure is represented by R in formula (1-1). 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in the following structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0403] [Chemical formula 30]

[0404]

[0405] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y 1 The group represented by the following formula (V-2-3) or formula (V-2-4) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-2-4) is preferred. X1 represents a single bond or -O-, * represents the same as Y in formula (1-1) 1 The bonding position of the two nitrogen atoms bonded. X1 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (1-1). 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0406] [Chemical Formula 31]

[0407]

[0408] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 1 The group represented by the following formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant, the group represented by formula (V-3-3) is preferred. In the following formula, * represents Y in formula (1-1). 1 The bonding position of the two nitrogen atoms bonded. X2 and R X3 The preferred embodiment is as described above. The n hydrogen atoms in the following structure are represented by R in formula (1-1). 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0409] [Chemical Formula 32]

[0410]

[0411] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 1 The group represented by the following formula (V-4-2) is preferred. In the following formula, * represents the same as Y in formula (1-1). 1 The bonding position of the two nitrogen atoms bonded, n1 represents an integer of 0 to 5. In addition, the embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. The number n of hydrogen atoms in the following structure is represented by R in formula (1-1). 1 The meaning of n is the same as that of n in formula (1-1). In addition, the hydrogen atoms in the following structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0412] [Chemical Formula 33]

[0413]

[0414] In addition, Y 1 It can be R in the above formula (4) 131 The group represented by is obtained by removing n hydrogen atoms.

[0415] And, Y 1 It is preferred that the structure does not contain an imide structure.

[0416] And, Y1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0417] In addition, Y 1 It is preferred that no ester bond be present in the structure.

[0418] Among these, Y 1 It is preferable that the polyol contains no imide structure, urethane bond, urea bond, or amide bond, and it is preferable that the polyol contains no imide structure, urethane bond, urea bond, amide bond, or ester bond.

[0419] Among these, X in formula (1-1) 1 and Y 1 It is preferable that each of the structures represented by any one of the above formulae (V-1) to (V-4) contain a structure in which two or more hydrogen atoms are removed.

[0420] In formula (1-1), m is an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which m is 0 is also one of the preferred embodiments of the present invention.

[0421] In formula (1-1), n ​​is preferably 1 or 2, more preferably 2.

[0422] The polyimide preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0423] To improve adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0424] In order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or an active monoester compound. Among these, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0425] -Imidization rate (ring closure rate)-

[0426] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

[0427] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0428] The imidization rate can be measured, for example, by the following method.

[0429] Measure the infrared absorption spectrum of polyimide and find the absorption peak at 1377 cm-1 derived from the imide structure. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0430] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0431] Polyimide can contain repeating units with all R 131 and R 132The repeating unit represented by the above formula (4) may also contain R 131 and R 132 The polyimide may contain two or more repeating units represented by the above formula (4) in combination with different repeating units. In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include repeating units represented by the following formula (2).

[0432] For example, polyimide can be obtained by reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent) at low temperature, reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with an acid anhydride or a monoacyl chloride compound or an active monoester compound, i.e., an end-capping agent) at low temperature, reacting a diester by tetracarboxylic dianhydride and an alcohol in the presence of a diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent) and a condensing agent, chlorinating the remaining dicarboxylic acid after obtaining a diester by tetracarboxylic dianhydride and an alcohol and reacting it with a diamine (a portion of which is substituted with a monoamine, i.e., an end-capping agent), and the like, and then completely imidizing it by a conventional imidization reaction method or stopping the imidization reaction midway and introducing a portion of an imide structure, or synthesizing it by further mixing a completely imidized polymer and its polyimide precursor to introduce a portion of an imide structure. In addition, other known methods for synthesizing polyimides can also be applied.

[0433] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, and even more preferably 7,000 to 20,000. The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 20,000, and even more preferably 4,000 to 10,000.

[0434] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0435] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide be within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight, and dispersity of the multiple polyimides, calculated as a single resin, be within the above ranges.

[0436] [Method for producing polyimide precursor, etc.]

[0437] For example, polyimide precursors and the like can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamic acid, and esterifying the obtained product with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the obtained product in the presence of a diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine is more preferred.

[0438] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0439] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0440] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0441] 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.

[0442] The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0443] In the method for producing a polyimide precursor, etc., it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0444] The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0445] -Capping agent-

[0446] In the manufacture method of polyimide precursor etc., in order to further improve storage stability, it is preferred to seal the carboxylic acid anhydride, anhydride derivative or amino group remaining in the resin end of polyimide precursor etc. When the carboxylic acid anhydride and anhydride derivative remaining in the resin end are end-blocked, as end-blocking agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be enumerated. From the perspective of reactivity and film stability, monoalcohol, phenols, monoamine are more preferably used. As the preferred compound of monoalcohol, methyl alcohol, ethanol, propyl alcohol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol and other primary alcohols, isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohol, tertiary alcohol, adamantane alcohol and other tertiary alcohols can be enumerated. As the preferred compound of phenols, phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene and other phenols can be enumerated. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a variety of different terminal groups may be introduced by reacting a variety of end-capping agents.

[0447] Moreover, when the amino group at the end of the resin is blocked, it is possible to block the end with a compound having a functional group that can react with the amino group. Preferred end-blocking agents for the amino group are preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic anhydride, sulfonic acid carboxylic anhydride, etc., more preferably carboxylic anhydride, carboxylic acid chloride. As preferred compounds of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be mentioned. And, as preferred compounds of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, valeryl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be mentioned.

[0448] -Solid precipitation-

[0449] In the manufacturing method of polyimide precursor etc., the process of solid precipitation can be included. Specifically, after filtering the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution as needed, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, thereby making it precipitate as a solid and dry to obtain polyimide precursor etc. In order to improve the degree of purification, the polyimide precursor etc. can be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. The process of removing ionic impurities using an ion exchange resin can also be further included.

[0450] 〔content〕

[0451] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0452] The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0453] It is also preferred that the resin composition of the present invention contains at least two resins.

[0454] Specifically, the resin composition of the present invention may contain two or more specific resins in total of the specific resin and other resins described below, or may contain two or more specific resins, and preferably contains two or more specific resins.

[0455] When the resin composition of the present invention contains two or more specific resins, for example, it is preferable to contain a structure derived from a dianhydride (R represented by the above formula (2)) which is a polyimide precursor. 115 ) Two or more different polyimide precursors.

[0456] <Other resins>

[0457] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0458] As other resins, other polyimide precursors different from the specific resin, polyimide, polybenzoxazole precursor, polybenzoxazole, polyamideimide precursor, polyamideimide, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylic amide resin, urethane resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. can be listed.

[0459] Examples of other polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355, all of which are incorporated herein by reference.

[0460] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0461] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0462] As a preferred embodiment of the resin composition of the present invention, a method in which the content of other resins is low can also be used. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0463] The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more other resins, the total amount is preferably within the above range.

[0464] <Polymerizable Compound>

[0465] The resin composition of the present invention preferably contains a polymerizable compound.

[0466] Furthermore, an embodiment in which the resin composition of the present invention contains a polymerizable compound and a photopolymerization initiator is also one of the preferred embodiments of the present invention.

[0467] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0468] 〔Free radical crosslinker〕

[0469] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0470] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferably included. As the above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be mentioned.

[0471] Among these, (meth)acryloyl, (meth)acrylamide, and vinylphenyl are preferred. From the perspective of reactivity, (meth)acryloyl is more preferred, and acryloyl is even more preferred. When using an acryloyloxy group, the structure after polymerization is less likely to depolymerize than other polymerizable groups such as a methacryloyloxy group, and thus it is believed that the flatness is better.

[0472] 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.

[0473] The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.

[0474] From the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0475] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0476] As the concrete example of free radical crosslinking agent, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) or its esters, amides can be enumerated, preferably the ester of unsaturated carboxylic acid and polyol compound and the amides of unsaturated carboxylic acid and polyamine compound.Also, it is also possible to preferably use the addition reaction product of unsaturated carboxylic acid ester or amides with monofunctional or polyfunctional isocyanates or epoxies with nucleophilic substituents such as hydroxyl, amino, thiol, and the dehydration condensation reaction product of monofunctional or polyfunctional carboxylic acid etc.Also, it is preferred to have the addition reaction product of unsaturated carboxylic acid ester or amides with monofunctional or polyfunctional alcohols, amines, thiols of the electrophilic substituents such as isocyanate group, epoxy group, and then also preferably have the substitution reaction product of unsaturated carboxylic acid ester or amides with monofunctional or polyfunctional alcohols, amines, thiols with the leaving property substituents such as halogen, p-toluenesulfonyloxy (tosyloxy group) and monofunctional or polyfunctional alcohols, amines, thiol. Furthermore, as another example, the unsaturated carboxylic acid may be replaced with a compound group substituted with an unsaturated phosphonic acid, styrene, or a vinylbenzene derivative, vinyl ether, or allyl ether. Specific examples include reference to paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference.

[0477] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher at normal pressure. Examples of compounds having a boiling point of 100° C. or higher at normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0478] Preferred radical crosslinking agents other than those mentioned above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, and the contents are incorporated into this specification.

[0479] Preferred radical crosslinking agents 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 structures in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. These oligomers can also be used.

[0480] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four vinyloxy chains; SR-209, 231, and 239, bifunctional methacrylates having four vinyloxy chains (all manufactured by Sartomer Company, Inc.); DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains; TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.); urethane oligomers UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (all manufactured by Nippon Kayaku Co., Ltd.). Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0481] Preferred free radical crosslinking agents include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Application Laid-Open No. 62-039417, and Japanese Patent Application Laid-Open No. 62-039418. Free radical crosslinking agents also include compounds having an amino structure or a thioether structure in the molecule, as described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238.

[0482] The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. Preferred free radical crosslinking agents having an acid group are esters of aliphatic polyols and unsaturated carboxylic acids. More preferred are free radical crosslinking agents obtained by reacting the unreacted hydroxyl groups of the aliphatic polyols with a non-aromatic carboxylic anhydride to impart acid groups. Particularly preferred are compounds obtained by reacting the unreacted hydroxyl groups of the aliphatic polyols with a non-aromatic carboxylic anhydride to impart acid groups, wherein the aliphatic polyol is pentaerythritol or dipentaerythritol. Examples of commercially available products include polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0483] The acid value of the radical crosslinking agent containing an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. A radical crosslinking agent with an acid value within this range provides excellent workability and developability during production. Furthermore, the polymerizability is good. The acid value is measured in accordance with JIS K 0070:1992.

[0484] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from a urea bond and a urethane bond (hereinafter also referred to as “crosslinking agent U”) is also preferred.

[0485] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom.

[0486] In the present invention, the urethane bond refers to the bond consisting of *-OC(=0)-NR N -* indicates a key, R Nrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding position to a carbon atom.

[0487] When the resin composition contains the crosslinking agent U, chemical resistance, resolution, etc. may be improved.

[0488] The mechanism by which the above effects are achieved is not clear, but it is thought that, for example, a portion of the crosslinking agent U is thermally decomposed during curing by heating, etc., thereby generating amines, etc., which promote the cyclization of a precursor of a cyclized resin such as a polyimide precursor.

[0489] The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have two or more urea bonds without a urethane bond, or may have two or more urethane bonds without a urea bond.

[0490] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0491] When the crosslinking agent U does not have a urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0492] When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0493] The free radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy.

[0494] When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different.

[0495] The number of radical polymerizable groups in the crosslinking agent U may be only one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0496] The radical polymerizable group value (mass of radical polymerizable groups per 1 mol of the compound) in the crosslinking agent U is preferably 150 to 400 g / mol.

[0497] From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0498] From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0499] The polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[0500] The crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.

[0501] [Chemical Formula 34]

[0502]

[0503] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1 valent organic group, X is a radical polymerizable group, n is an integer of 1 or greater, and m is an integer of 1 or greater.

[0504] R U1 A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0505] R N A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0506] Z U1 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[0507] The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and further preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds of these groups. N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group.

[0508] Z U2 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of

[0509] Examples of the hydrocarbon group include U1 The same as those mentioned above have the same preferred embodiments.

[0510] X is not particularly limited and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. Preferred are (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. More preferred are (meth)acryloyloxy.

[0511] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0512] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0513] The crosslinking agent U preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[0514] From the viewpoint of chemical resistance of the obtained cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but is preferably an alcoholic hydroxyl group.

[0515] From the viewpoint of chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, further preferably an alkyleneoxy group having 2 to 4 carbon atoms, further preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

[0516] The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, more preferably 2 to 6.

[0517] Amide refers to -C(=O)-NR N - represents the bond. N When the crosslinking agent U has an amide group, the crosslinking agent U can contain an amide group as a RC(=O)-NR N -* or a group represented by *-C(=O)-NR N - A group represented by R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0518] The crosslinking agent U may have two or more structures selected from the group consisting of hydroxyl groups, alkyleneoxy groups (polyalkyleneoxy groups when forming polyalkyleneoxy groups), amide groups, and cyano groups in the molecule, but preferably has only one structure in the molecule.

[0519] The above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. However, from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group is linked to at least one radical polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[0520] In particular, when the crosslinking agent U contains only one free radical polymerizing group, it is preferred that the free radical polymerizing group contained in the crosslinking agent U is linked to at least one selected from a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[0521] When the crosslinking agent U contains an alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferred, a hydrocarbon group having 18 or less carbon atoms is more preferred, and a hydrocarbon group having 16 or less carbon atoms is further preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these can be cited. In addition, the preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U.

[0522] When the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. As the above-mentioned hydrocarbon group, a hydrocarbon group with 20 or less carbon atoms is preferred, a hydrocarbon group with 18 or less carbon atoms is more preferred, and a hydrocarbon group with 16 or less carbon atoms is further preferred. In addition, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these can be cited. The preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U. In addition, in the above embodiment, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2.

[0523] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferred that the crosslinking agent U has a hydroxyl group.

[0524] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group.

[0525] The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferred that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0526] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may be a structure in which these groups form a condensed ring, but is preferably an aromatic hydrocarbon group.

[0527] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably a group formed by removing two or more hydrogen atoms from a benzene ring structure.

[0528] The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole.

[0529] As the hetero atom contained in the aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[0530] The aromatic group is preferably contained in a linking group that is linked to two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U.

[0531] The number of atoms (linked chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2-20, and even more preferably 2-10.

[0532] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, in the case of containing two or more free radical polymerizable groups, or in the case of containing two or more urea bonds or urethane bonds and containing two or more free radical polymerizable groups, the minimum number of atoms among the number of atoms of the urea bond or urethane bond and the free radical polymerizable group (linked chain length) may be within the above range.

[0533] In this specification, the term "the number of atoms (chain length) between a urea bond or urethane bond and a polymerizable group" refers to the shortest (smallest) atomic chain connecting two atoms or groups of atoms to be linked. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the radically polymerizable group (methacryloyloxy group) is 2.

[0534] [Chemical Formula 35]

[0535]

[0536] 〔Axis of symmetry〕

[0537] The crosslinking agent U is also preferably a compound having a structure without an axis of symmetry.

[0538] Crosslinker U lacking an axis of symmetry means that the compound is bilaterally asymmetric and lacks an axis that would produce a molecule identical to the original molecule upon rotation of the entire compound. Furthermore, when noting the structural formula of crosslinker U on paper, "crosslinker U lacking an axis of symmetry" means that the structural formula of crosslinker U cannot be expressed as having an axis of symmetry.

[0539] Since the cross-linking agent U does not have a symmetric axis, it is considered that aggregation of the cross-linking agents U in the composition film is suppressed.

[0540] 〔Molecular weight〕

[0541] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and more preferably 200 to 900.

[0542] The method for producing the crosslinking agent U is not particularly limited, and for example, the crosslinking agent U can be obtained by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group and an amino group.

[0543] The following are specific examples of the crosslinking agent U, but the crosslinking agent U is not limited thereto.

[0544] [Chemical Formula 36]

[0545]

[0546] [Chemical Formula 37]

[0547]

[0548] [Chemical Formula 38]

[0549]

[0550] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate in the resin composition.

[0551] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, Alkene esters, 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 adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid-modified diacrylate, isocyanuric acid-EO-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond. These can be used in combination of two or more as needed.

[0552] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of approximately 200.

[0553] From the viewpoint of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent. As a monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, mono(meth)acrylate polyethylene glycol, mono(meth)acrylate polypropylene glycol, (meth)acrylate derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other (meth) acrylic acid derivatives, allyl glycidyl ether. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, it is also preferred to use a compound having a boiling point of 100°C or more at normal pressure.

[0554] Examples of bifunctional or higher-functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0555] When a free radical crosslinking agent is included, the content of the free radical crosslinking agent is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0556] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[0557] 〔Other crosslinking agents〕

[0558] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0559] The other crosslinking agent refers to a crosslinking agent other than the above-mentioned free radical crosslinking agent, and is preferably a compound having multiple groups in the molecule that accelerate the reaction (forming a covalent bond with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably a compound having multiple groups in the molecule that accelerate the reaction (forming a covalent bond with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0560] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0561] As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0562] Other crosslinking agents include, for example, compounds having a structure obtained by reacting an amino group-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, or benzoguanamine with formaldehyde, or by reacting formaldehyde with an alcohol, with the hydrogen atoms of the amino group being substituted with acyloxymethyl, hydroxymethyl, hydroxyethyl, or alkoxymethyl groups. The production methods for these compounds are not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. These compounds may also be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[0563] As the above-mentioned amino-containing compound, a cross-linking agent using melamine is referred to as a melamine-based cross-linking agent, a cross-linking agent using acetylene carbamide, urea or alkylene urea is referred to as a urea-based cross-linking agent, a cross-linking agent using alkylene urea is referred to as an alkylene urea-based cross-linking agent, and a cross-linking agent using benzoguanamine is referred to as a benzoguanamine-based cross-linking agent.

[0564] Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0565] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the following urea structure, or a triazine.

[0566] The alkoxymethyl group or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms.

[0567] The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0568] The molecular weight of the compound is preferably 1500 or less, more preferably 180 to 1200.

[0569] [Chemical Formula 39]

[0570]

[0571] R 100 represents an alkyl group or an acyl group.

[0572] R 101 and R 102 Each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0573] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula.

[0574] [Chemical Formula 40]

[0575]

[0576] In the formula, X represents a single bond or a divalent organic group, each R 104 Each independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that leaves by the action of an acid, a group consisting of -C(R 4 )2COOR 5 The group represented by (R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 It represents a group that leaves by the action of an acid.

[0577] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0578] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that leaves by the action of an acid, the group consisting of -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0579] Where R 36 ~R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0580] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0581] The alkyl group may be linear or branched.

[0582] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[0583] The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

[0584] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0585] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[0586] The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as those of the above-mentioned alkyl groups and aryl groups.

[0587] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0588] These groups may further have a known substituent.

[0589] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0590] As the group that decomposes by the action of an acid to generate an alkali-soluble group or the group that leaves by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0591] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. Preferred embodiments of the above-mentioned compound are the same as those of the crosslinking agent U, except that the polymerizable group is at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, and an alkoxymethyl group, rather than a radical polymerizable group.

[0592] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and a hydroxyethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is replaced with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

[0593] [Chemical Formula 41]

[0594]

[0595] [Chemical Formula 42]

[0596]

[0597] [Chemical Formula 43]

[0598]

[0599] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product may be used, or a compound synthesized by a known method may be used.

[0600] From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0601] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0602] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxymethylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide.

[0603] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0604] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[0605] Propylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[0606] 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0607] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0608] Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0609] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Benzophenone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0610] As other cross-linking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Yukizai Corporation), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[0611] The resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0612] -Epoxy compound (compound having an epoxy group)-

[0613] Epoxy compounds preferably have two or more epoxy groups per molecule. Epoxy groups undergo cross-linking reactions below 200°C and do not induce dehydration during cross-linking, thus minimizing film shrinkage. Therefore, the inclusion of epoxy compounds effectively suppresses low-temperature curing and warping of the resin composition.

[0614] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

[0615] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specific examples include EPICLON (registered trademark, the same shall apply hereinafter) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON HP-4770, EPICLON EXA-830LVP, EPICLON EXA-8183, EPICLON EXA-8169, EPICLON N-660, EPICLON N-665-EXP-S, and EPICLON N-740 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark, the same shall apply hereinafter) BEO-20E, RIKARESIN BEO-60E, RIKARESIN HBE-100, RIKARESIN DME-100, and RIKARESIN L-200 (these are trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark, hereinafter the same) 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EPOLEAD (registered trademark, hereinafter the same) GT401, EPOLEAD PB4700, EPOLEAD PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (these are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[0616] [Chemical Formula 44]

[0617]

[0618] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0619] In the above structure, from the viewpoint of achieving both heat resistance and improvement in elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[0620] -Oxetane compound (compound containing oxetane compound)-

[0621] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the ARON OXETANE series (e.g., OXT-121 and OXT-221) manufactured by Toagosei Co., Ltd. These compounds may be used alone or in combination of two or more.

[0622] -Benzoxazine compound (compound having a benzoxazolyl group)-

[0623] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a crosslinking reaction caused by a ring-opening addition reaction and also reduce thermal shrinkage to suppress the occurrence of warping.

[0624] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0625] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solids content of the resin composition. The other crosslinking agent may be contained in a single species or in two or more species. When two or more other thermal crosslinking agents are contained, their total preferably falls within the above range.

[0626] 〔Polymerization initiator〕

[0627] The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferred to contain a photopolymerization initiator.

[0628] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active free radicals may be used.

[0629] Furthermore, the polymerization initiator is preferably a photoacid generator. As the photoacid generator, a photoacid generator that generates free radicals is preferred.

[0630] The photoradical polymerization initiator preferably contains at least one having a photocatalytic activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1 The molar absorptivity of a compound can be determined using known methods. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate as a solvent at a concentration of 0.01 g / L.

[0631] As a photoradical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. In addition, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent Application No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313. These contents are incorporated into this specification.

[0632] Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0633] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents of these initiators are incorporated into this specification.

[0634] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0635] As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0636] As aminoacetophenone-based initiators, acylphosphine oxide-based initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. This content is incorporated into this specification.

[0637] Oxime compounds are more preferably used as photoradical polymerization initiators. Oxime compounds can further effectively improve exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0638] Specific examples of oxime compounds 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 JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Laid-Open No. 2000-066385, compounds described in Japanese Translation of PCT International Publication No. 2004-534797, compounds described in Japanese Patent Application Laid-Open No. 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 Japanese Patent Application Laid-Open No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and the like, the contents of which are incorporated into this specification.

[0639] Preferred oxime compounds include, for example, compounds having the following structures: 3-(benzoyloxy(imino)butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. Oxime compounds serving as photoradical polymerization initiators have a linking group >C=NOC(=O)- in the molecule.

[0640] [Chemical Formula 45]

[0641]

[0642] Commercially available products of oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, a photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304, TR-PBG-305, and TR-PBG-3057 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by Sartomer Arkema). Oxime compounds having the following structures can also be used.

[0643] [Chemical Formula 46]

[0644]

[0645] As the photoradical polymerization initiator, for example, oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can also be used.

[0646] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxyl group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These contents are incorporated into this specification.

[0647] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. 0X1 As the aromatic ring group Ar 0X1Examples of the electron-withdrawing group include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups. Acyl and nitro groups are preferred. From the perspective of ease of forming a film with excellent light resistance, acyl groups are more preferred, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclicoxy group, alkenyl, alkylsulfanyl, arylsulfanyl, acyl, or amino group. An alkyl, alkoxy, aryl, aryloxy, heterocyclicoxy group, alkylsulfanyl, arylsulfanyl, or amino group is more preferred. An alkoxy, alkylsulfanyl, or amino group is even more preferred.

[0648] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and more preferably a compound represented by the formula (OX2).

[0649] [Chemical Formula 47]

[0650]

[0651] Where R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfamoyl group,

[0652] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

[0653] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0654] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0655] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 、R X11 、R X13 、R X14 A hydrogen atom.

[0656] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

[0657] Particularly preferred oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like, the contents of which are incorporated herein.

[0658] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0659] Furthermore, the photoradical polymerization initiator is a trihalomethyl triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, and a benzophenone compound, further preferably a metallocene compound or an oxime compound.

[0660] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents thereof are incorporated into this specification.

[0661] As the photoradical polymerization initiator, a photoradical polymerization initiator having difunctional or trifunctional functions or more can be used. By using this type of photoradical polymerization initiator, more than two free radicals are generated from a molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound of an asymmetric structure is used, crystallinity decreases and the solubility in a solvent etc. becomes higher, becomes difficult for precipitation over time, and thus can improve the time stability of resin combination. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds (E) and ( G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[0662] When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may be contained in a single species or in two or more species. When containing two or more photopolymerization initiators, the total amount is preferably within the above range.

[0663] In addition, a photopolymerization initiator may also function as a thermal polymerization initiator. Therefore, heating in an oven, hot plate, or the like may further promote crosslinking by the photopolymerization initiator.

[0664] 〔Sensitizer〕

[0665] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, electron transfer, energy transfer, and heat generation occur. This chemically changes the thermal radical polymerization initiator or the photoradical polymerization initiator, causing it to decompose and generate free radicals, acids, or bases.

[0666] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzyl (benzylidene), oXonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0667] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamindanone, p-dimethylaminoindanone, and 4,4'-bis(dimethylamino)chalcone. Benzyl indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl -7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino isopentyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0668] Furthermore, other sensitizing dyes can also be used.

[0669] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[0670] 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 even more preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0671] Chain transfer agent

[0672] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) on pages 683-684. As chain transfer agents, for example, a compound group having -SS-, -SO2-S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, etc. can be used. These can generate free radicals by donating hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0673] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into this specification.

[0674] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be a single type or two or more types. When two or more chain transfer agents are used, their total preferably falls within the above range.

[0675] <Alkali Generator>

[0676] The resin composition of the present invention may contain a base generator. Here, a base generator refers to a compound that can generate a base through physical or chemical action. Preferred base generators include thermal base generators and photobase generators.

[0677] In particular, when the resin composition contains a precursor for a cyclized resin, it is preferred that the resin composition contain a base generator. The inclusion of a thermal base generator in the resin composition can accelerate the cyclization reaction of the precursor, for example, by heating, resulting in a cured product having excellent mechanical properties and chemical resistance. This improves the performance of, for example, an interlayer insulating film for a redistribution layer included in a semiconductor package.

[0678] The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.

[0679] The base generator is not particularly limited, and a known base generator can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imide salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0680] Specific examples of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

[0681] [Chemical Formula 48]

[0682]

[0683] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 Each independently represents an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 Not all of them have carboxyl groups. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, when the carbon atom bonded to a trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when it forms an amide group with the nitrogen atom, it is not a tertiary amine structure.

[0684] In formulas (B1) and (B2), Rb is preferably 1 , Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. The cyclic structure may be any of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0685] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12 carbon atoms). These groups may have a substituent. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Preferred is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have a substituent.

[0686] As Rb 3 , examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), arylalkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and arylalkoxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferred. 3 It may further have a substituent.

[0687] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0688] [Chemical Formula 49]

[0689]

[0690] Where Rb 11 and Rb 12 and Rb31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 same.

[0691] Rb 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent. 13 Aralkyl groups are preferred.

[0692] Rb 33 and Rb 34 Each of them is independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), preferably a hydrogen atom.

[0693] Rb 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), preferably an aryl group.

[0694] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0695] [Chemical Formula 50]

[0696]

[0697] Rb 11 and Rb 12 The meaning is the same as Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0698] Rb 15 and Rb 16It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), preferably a hydrogen atom or a methyl group.

[0699] Rb 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0700] [Chemical Formula 51]

[0701]

[0702] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain connecting adjacent oxygen atoms and carbon atoms and having 3 or more atoms on the linking chain. N1 and R N2 Each independently represents a monovalent organic group.

[0703] In this specification, the term "linking chain" refers to a chain of atoms on a path connecting two atoms or groups of atoms that are to be linked, connecting these linked objects along the shortest path (minimum number of atoms). For example, in a compound represented by the following formula, L is composed of phenyleneethylene and has ethylene as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.

[0704] [Chemical Formula 52]

[0705]

[0706] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly proceeding with the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds as alkali generators include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0707] Furthermore, the base generating agent preferably also contains a compound represented by the following formula (N1).

[0708] [Chemical Formula 53]

[0709]

[0710] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0711] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably more than 1, more preferably more than 2. As an upper limit, it is preferably less than 12, more preferably less than 8, and further preferably less than 5. The linking chain length refers to the number of atoms present in the atomic arrangement, and the atomic arrangement becomes the shortest distance between the two carbonyl groups in the formula.

[0712] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), preferably an aliphatic hydrocarbon group. When an aliphatic hydrocarbon group is used as R N1 and R N2, the basicity of the generated base is high, so it is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

[0713] As a component of R N1 and R N2 Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups, cyclic alkyl groups, groups comprising a combination of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The linear or branched alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0714] The number of carbon atoms in the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0715] The number of carbon atoms in the group comprising a combination of a chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group comprising a combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0716] The number of carbon atoms in the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like, cyclic, linear, or branched.

[0717] However, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 An alkyl group having 5 to 12 carbon atoms is preferred. However, in a formulation where adhesion to a metal (eg, copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0718] R N1 and R N2 The ring structure may have oxygen atoms in the chain. N1 and R N2The cyclic structure formed can be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. As the cyclic structure formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. can be mentioned, and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring can be mentioned.

[0719] R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0720] As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid is preferably used.

[0721] As a specific example of the protecting group, a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain can be enumerated. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. can be enumerated. As a chain alkyl group having an oxygen atom in the chain, an alkoxyalkyl group, preferably a methoxymethyl (MOM) group, an ethoxyethyl (EE) group, etc. can be enumerated. As a cyclic alkyl group having an oxygen atom in the chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group, etc. can be enumerated.

[0722] In formula (N1), the divalent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, further preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, further preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.

[0723] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., an aralkylene group) is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0724] Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group comprising a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

[0725] The number of carbon atoms in the linear or branched alkylene group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4.

[0726] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

[0727] The number of carbon atoms in the group consisting of a combination of a chain alkylene group and a cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0728] The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be linear or branched. The number of carbon atoms in the alkylene group having an oxygen atom in its chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0729] The number of carbon atoms in the linear or branched alkenylene group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0730] The number of carbon atoms in the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of C═C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0731] The arylene group has preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms.

[0732] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.

[0733] Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylenealkylene groups; more preferred are 1,2-ethylene, propylene (particularly 1,3-propylene), cyclohexanediyl (particularly 1,2-cyclohexanediyl), vinylene (particularly cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (particularly 1,2-phenylenemethylene), and ethyleneoxyethylene (particularly 1,2-ethyleneoxy-1,2-ethylene).

[0734] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0735] [Chemical Formula 54]

[0736]

[0737] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0738] Specific examples of preferred compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0739] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0740] [Chemical Formula 55]

[0741]

[0742] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0743] [Chemical Formula 56]

[0744]

[0745] Furthermore, as the base generator, an amine in which the amino group is protected by a tert-butoxycarbonyl group is preferred from the viewpoints of storage stability and deprotection during sulfurization to generate a base.

[0746] Examples of the amine compound protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl] Benzyl alcohol, diethanolamine, diisopropanolamine, 3-hydroxypyrrolidine, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidine)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetrahydrotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or amino acids and compounds in which the amino groups of the derivatives are protected with tert-butoxycarbonyl groups, but are not limited thereto.

[0747] When the resin composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0748] The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

[0749] <Solvent>

[0750] The resin composition of the present invention preferably contains a solvent.

[0751] Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, carbonates, amides, ureas, and alcohols.

[0752] Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, cyclohexyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Preferred esters include 2-alkoxyalkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0753] Preferred examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0754] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, 4-methyl ethyl ketone, levoglucosenone, and dihydrolevoglucosenone.

[0755] Examples of the cyclic hydrocarbons preferably include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0756] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred sulfoxide.

[0757] As the carbonates, for example, propylene carbonate can be mentioned as a preferred carbonate.

[0758] As amides, 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, 2-hydroxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferred amides.

[0759] Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0760] Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0761] From the viewpoint of improving the properties of the coated surface, a mixture of two or more solvents is also preferred.

[0762] In the present invention, preferably, it is a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levulinone and dihydrolevulinone, or a mixed solvent consisting of two or more thereof. Particularly preferred are the simultaneous use of dimethyl sulfoxide and γ-butyrolactone, the simultaneous use of dimethyl sulfoxide and γ-valerolactone, the simultaneous use of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the simultaneous use of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone, and dimethyl sulfoxide, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate. Furthermore, one preferred embodiment of the present invention is the addition of approximately 1 to 10% by mass of toluene relative to the total mass of the solvent to these solvents.

[0763] Particularly, from the viewpoint of the storage stability of resin combination etc., the mode that comprises gamma-valerolactone as solvent is also one of preferred embodiment of the present invention.In this type of mode, the content of gamma-valerolactone relative to the gross mass of solvent is preferably more than 50 mass %, more preferably more than 60 mass %, further preferably more than 70 mass %.And, the upper limit of above-mentioned content is not particularly limited, can be 100 mass %.Above-mentioned content considers that the solubility of the composition such as the specific resin that comprises in resin combination etc. is determined.

[0764] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used simultaneously, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide.

[0765] The resin composition of the present invention preferably contains a solvent having a boiling point of 180° C. or lower from the viewpoints of facilitating solvent removal during drying, suppressing film shrinkage during the heating step due to volatilization of residual solvent, and improving flatness of the cured product.

[0766] Examples of the solvent having a boiling point of 180° C. or lower include ethyl lactate, cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcyclohexanone, 3-methylcyclohexanone, anisole, and cyclohexyl acetate.

[0767] The solvent having a boiling point of 180° C. or lower may be used alone or in combination of two or more.

[0768] Furthermore, from the viewpoint of adjusting the drying speed and improving the coating uniformity within the wafer surface, it is preferable to contain a solvent having a boiling point of 180° C. or lower and a solvent having a boiling point of more than 180° C.

[0769] Examples of such methods include the combined use of N-methyl-2-pyrrolidone and ethyl lactate, the combined use of N-methyl-2-pyrrolidone and cyclopentanone, the combined use of γ-butyrolactone and cyclopentanone, the combined use of γ-valerolactone and cyclopentanone, and the combined use of propylene carbonate and cyclopentanone.

[0770] In the above embodiment, relative to the total mass of the solvent, it is preferred that 40 to 90% by mass of a solvent having a boiling point of 180°C or less and 10 to 60% by mass of a solvent having a boiling point of more than 180°C are contained, more preferably 50 to 90% by mass of a solvent having a boiling point of 180°C or less and 10 to 50% by mass of a solvent having a boiling point of more than 180°C are contained, and further preferably 60 to 85% by mass of a solvent having a boiling point of 180°C or less and 15 to 40% by mass of a solvent having a boiling point of more than 180°C are contained.

[0771] In the above embodiment, the solvent having a boiling point of 180° C. or lower may be used alone or in combination of two or more. When two or more solvents are used in combination, the total amount thereof is preferably within the above range.

[0772] In the above embodiment, the solvent having a boiling point exceeding 180° C. may be used alone or in combination of two or more. When two or more solvents are used in combination, the total amount thereof is preferably within the above range.

[0773] From the viewpoint of coating properties, the content of the solvent is preferably set to an amount such that the total solid content concentration of the resin composition of the present invention reaches 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the thickness required for the coating film and the coating method. When containing two or more solvents, it is preferred that the total amount thereof is within the above range.

[0774] <Metal Adhesion Improver>

[0775] From the perspective of improving adhesion to metal materials used in electrodes, wiring, etc., the resin composition of the present invention preferably contains a metal adhesion improver. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[0776] 〔Silane coupling agent〕

[0777] As silane coupling agents, for example, the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 can be cited, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferred to use two or more different silane coupling agents. The following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can be a structure derived from a blocking agent in a blocked isocyanate group. As a blocking agent, it can be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like. For example, from the perspective of setting the desorption temperature to 160 to 180°C, caprolactam and the like are preferred. Examples of commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0778] [Chemical Formula 57]

[0779]

[0780] Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediaminetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0781] Furthermore, as the silane coupling agent, an oligomer-type compound having a plurality of alkoxysilyl groups can also be used.

[0782] Examples of such oligomer compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0783] [Chemical Formula 58]

[0784]

[0785] In formula (S-1), R S1 represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.

[0786] R S1 Preferably there is a structure containing a polymerizable group. As a polymerizable group, a group with an ethylenically unsaturated bond, an epoxy group, an oxycyclobutane group, a benzoxazolyl group, a blocked isocyanate group, an amino group can be enumerated. As a group with an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group (for example, vinylphenyl etc.) with an aromatic ring directly bonded to a vinyl group, (methyl) acrylamide, (methyl) acryloyloxy etc. can be enumerated, preferably vinylphenyl, (methyl) acrylamide or (methyl) acryloyloxy, more preferably vinylphenyl or (methyl) acryloyloxy, further preferably (methyl) acryloyloxy.

[0787] R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

[0788] n represents an integer of 0 to 2, and is preferably 1.

[0789] Here, the structures of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound may be the same.

[0790] Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer type compound, n is preferably 1 or 2 in at least one, more preferably 1 or 2 in at least two, and even more preferably 1 in at least two.

[0791] As such oligomer type compounds, commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0792] 〔Aluminum-based adhesive〕

[0793] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0794] As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and these contents are incorporated into this specification.

[0795] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one or two or more. When two or more are used, their total is preferably within the above range.

[0796] <Migration Inhibitor>

[0797] The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0798] The migration inhibitor is not particularly limited, and examples thereof 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, 6H-pyran ring, triazine ring), compounds having thiourea and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0799] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0800] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015 / 199219 can be used, and these contents are incorporated into this specification.

[0801] Specific examples of the migration inhibitor include the following compounds.

[0802] [Chemical Formula 59]

[0803]

[0804] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0805] The migration inhibitor may be one or two or more. When two or more migration inhibitors are used, the total amount thereof is preferably within the above range.

[0806] <Light absorber>

[0807] The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases due to exposure.

[0808] Whether or not Compound a contained in the resin composition is a light absorber (that is, whether or not the absorbance at the exposure wavelength decreases due to exposure) can be determined by the following method.

[0809] First, a solution of compound a having the same concentration as that contained in the resin composition was prepared, and the molar absorption coefficient (mol -1 ·L·cm -1 , also referred to as "molar absorption coefficient 1". ). In order to reduce the influence of changes such as a decrease in the molar absorption coefficient of compound a, the above-mentioned measurement is performed quickly. Regarding the solvent in the above-mentioned solution, when the resin composition contains a solvent, the solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.

[0810] Next, the solution of Compound a was irradiated with exposure light at a cumulative exposure dose of 500 mJ per mol of Compound a.

[0811] Then, the molar absorption coefficient (mol -1 ·L·cm -1 , also known as the "molar absorptivity 2". ).

[0812] The attenuation rate (%) is calculated from the above-mentioned molar absorption coefficient 1 and molar absorption coefficient 2 according to the following formula. When the attenuation rate (%) is 5% or more, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases upon exposure (i.e., a light absorber).

[0813] Attenuation rate (%) = 1-molar absorption coefficient 2 / molar absorption coefficient 1×100

[0814] The attenuation rate is preferably 10% or higher, more preferably 20% or higher. The lower limit of the attenuation rate is not particularly limited, and may be 0% or higher.

[0815] The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form the photosensitive film.

[0816] The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive. The photopolymerization initiator being sensitive to a certain wavelength means that polymerization initiating species are generated when the photopolymerization initiator is exposed to a certain wavelength.

[0817] As the wavelength of the above-mentioned exposure light, in terms of its relationship with the light source, there are (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc.

[0818] The wavelength of the exposure light may be any wavelength to which the photopolymerization initiator is sensitive, and h-rays (wavelength 405 nm) or i-rays (wavelength 365 nm) are preferred, and i-rays (wavelength 365 nm) are more preferred.

[0819] The light absorber may be a compound that generates a radical polymerization initiating species upon exposure, but is preferably a compound that does not generate a radical polymerization initiating species upon exposure from the viewpoint of resolution and chemical resistance.

[0820] Whether or not the light absorber is a compound that generates a radical polymerization initiating species upon exposure can be determined by the following method.

[0821] Prepare a solution containing a light absorber and a radical crosslinker at the same concentrations as those in the resin composition. If the resin composition contains a radical crosslinker, use the same compound as the radical crosslinker in the solution at the same concentration. If the resin composition does not contain a radical crosslinker, use methyl methacrylate at a concentration five times that of the light absorber.

[0822] Thereafter, exposure light was irradiated, and the accumulated exposure amount was set to 500 mJ.

[0823] After exposure, polymerization of the polymerizable compound is determined, for example, by high-performance liquid chromatography. If the ratio of the molar amount of the polymerizable compound that has polymerized relative to the total molar amount of the polymerizable compound is 10% or less, the light absorber is determined to be a compound that does not generate radical polymerization initiating species by exposure.

[0824] The above-mentioned molar ratio is preferably 5% or less, more preferably 3% or less. The lower limit of the above-mentioned molar ratio is not particularly limited and may be 0%.

[0825] The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form the photosensitive film.

[0826] Furthermore, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

[0827] Examples of compounds that generate radical polymerization initiating species upon exposure include the same compounds as those described above for the photoradical polymerization initiators. When the composition contains a photoradical polymerization initiator as a light absorber, the compound with the lowest polymerization initiating ability of the generated radical species is used as the light absorber, and the other compounds are used as photopolymerization initiators.

[0828] Examples of the compound that does not generate a radical polymerization initiating species by exposure include, in addition to a photoacid generator and a photobase generator, a dye whose absorption wavelength changes by exposure.

[0829] Among them, the light absorber is preferably naphthoquinone diazide or a dye whose absorbance changes upon exposure, and more preferably naphthoquinone diazide.

[0830] Furthermore, as the light absorber, for example, it is also conceivable to use a photoacid generator or a photobase generator in combination with a compound whose absorbance at the exposure wavelength decreases depending on pH.

[0831] 〔Naphthoquinone diazide〕

[0832] Examples of the naphthoquinonediazide include compounds that generate indenecarboxylic acid upon exposure and whose absorbance at the exposure wavelength decreases, and compounds having a 1,2-naphthoquinonediazide structure are preferred.

[0833] As the naphthoquinone diazide compound, naphthoquinone diazide sulfonic acid ester of a hydroxy compound is preferred.

[0834] As the hydroxy compound, a compound represented by any one of the following formulae (H1) to (H6) is preferred.

[0835] [Chemical Formula 60]

[0836]

[0837] In formula (H1), R 1 and R 2 Each independently represents a monovalent organic group, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group; n1, n2, m1, and m2 each independently represent an integer of 0 to 5; and at least one of m1 and m2 represents an integer of 1 to 5.

[0838] In formula (H2), Z represents a tetravalent organic group, L 1 、L 2 、L 3 and L 4 Each independently represents a single bond or a divalent organic group, R 5 、R 6 、R 7 and R 8 Each independently represents a monovalent organic group, n3, n4, n5 and n6 are each independently an integer of 0 to 3, m3, m4, m5 and m6 are each independently an integer of 0 to 2, and at least one of m3, m4, m5 and mδ is 1 or 2.

[0839] In formula (H3), R 9 and R 10 Each independently represents a hydrogen atom or a monovalent organic group, L 5 Each independently represents a divalent organic group, and n7 represents an integer of 3-8.

[0840] In formula (H4), L 6 Represents a divalent organic group, L 7 and L 8Each independently represents a divalent organic group containing an aliphatic tertiary carbon atom or a quaternary carbon atom.

[0841] In formula (H5), R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, L 9 、L 10 and L 11 Each independently represents a single bond or a divalent organic group; m7, m8, m9, and m10 each independently represent an integer from 0 to 2; and at least one of m7, m8, m9, and m10 is 1 or 2.

[0842] In formula (H6), R 42 、R 43 、R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, R 46 and R 47 Each independently represents a monovalent organic group, n16 and n17 each independently represent an integer of 0 to 4, m11 and m12 each independently represent an integer of 0 to 4, and at least one of m11 and m12 is an integer of 1 to 4.

[0843] In formula (H1), R 1 and R 2 Each of the above groups is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 1 and R 2 The monovalent organic group in may be a hydrocarbon group which may have a substituent, for example, an aromatic hydrocarbon group which may have a substituent such as a hydroxyl group.

[0844] In formula (H1), R3 and R4 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. 3 and R 4 The monovalent organic group in may be a hydrocarbon group which may have a substituent, for example, a hydrocarbon group which may have a substituent such as a hydroxyl group.

[0845] In formula (H1), n1 and n2 are each independently preferably 0 or 1, more preferably 0.

[0846] In formula (H1), both ml and m2 are preferably 1.

[0847] The compound represented by formula (H1) is preferably a compound represented by any one of formulas (H1-1) to (H1-5).

[0848] [Chemical Formula 61]

[0849]

[0850] In formula (H1-1), R 21 、R 22 and R 23 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a group represented by the following formula (R-1).

[0851] [Chemical Formula 62]

[0852]

[0853] In formula (R-1), R 29 represents a hydrogen atom, an alkyl group or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding site with other structures.

[0854] In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.

[0855] In formula (H1-2), R 24 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15, and n16 each independently represent an integer of 0 to 2. 30 represents a hydrogen atom or an alkyl group.

[0856] In formula (H1-3), R 25 、R 26 、R 27 and R 28 Each independently represents a monovalent organic group, preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1).

[0857] In formula (H1-3), n11, n12, and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0858] As the compound represented by formula (H1-1), a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4) is preferred.

[0859] As the compound represented by formula (H1-2), a compound represented by the following formula (H1-2-1) or (H1-2-2) is preferable.

[0860] As the compound represented by formula (H1-3), compounds represented by the following formulas (H1-3-1) to (H1-3-3) are preferred.

[0861] [Chemical Formula 63]

[0862]

[0863] In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulas (Z-1) to (Z-4). In the following formulas (Z-1) to (Z-4), * represents a bonding site to another structure.

[0864] [Chemical Formula 64]

[0865]

[0866] In formula (H2), L 1 、L 2 、L 3 and L 4 Each independently preferably represents a single bond or a methylene group.

[0867] In formula (H2), R 5 、R 6 、R 7 and R 8 Each independently preferably is an organic group having 1 to 30 carbon atoms.

[0868] In formula (H2), n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0869] In formula (H2), m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1.

[0870] Examples of the compound represented by formula (H2) include compounds having the following structures.

[0871] [Chemical Formula 65]

[0872]

[0873] In formula (H3), R 9 and R 10 Each independently preferably represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0874] In formula (H3), L 5 Each independently preferably is a group represented by the following formula (L-1).

[0875] [Chemical Formula 66]

[0876]

[0877] In formula (L-1), R 30 represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding site with other structures.

[0878] In formula (H3), n7 is preferably an integer of 4-6.

[0879] Examples of the compound represented by formula (H3) include the following compounds: In the following formula, n each independently represents an integer of 0 to 9.

[0880] [Chemical Formula 67]

[0881]

[0882] In formula (H4), L 6 Preferred is -C(CF3)2-, -S(=0)2- or -C(=0)-.

[0883] In formula (H4), L 7 and L 8 Each independently is preferably a divalent organic group having 2 to 20 carbon atoms.

[0884] As the compound represented by formula (H4), the following compounds can be exemplified.

[0885] [Chemical Formula 68]

[0886]

[0887] In formula (H5), R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R17、R 18 、R 19 and R 20 Each independently preferably represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group.

[0888] In formula (H5), L 9 、L 10 and L 11 Each of them is independently preferably a single bond, -0-, -S-, -S(=O)2-, -C(=O)-, -C(=O)O-, a cyclopentylene group, a cyclohexylene group, a phenylene group or a divalent organic group having 1 to 20 carbon atoms, and more preferably a group represented by any one of the following formulas (L-2) to (L-4).

[0889] [Chemical Formula 69]

[0890]

[0891] In formula (L-2) to formula (L-4), R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R 34 、R 35 、R 36 and R 37 Each independently represents a hydrogen atom or an alkyl group, n15 is an integer from 1 to 5, R 38 、R 39 、R 40 and R 41 Each independently represents a hydrogen atom or an alkyl group, and * represents a bonding site to another structure.

[0892] Examples of the compound represented by formula (H5) include the following compounds.

[0893] [Chemical Formula 70]

[0894]

[0895] In formula (H6), R 42 、R 43 、R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0896] In formula (H6), R 46 and R 47 Each independently is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.

[0897] In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0898] In formula (H6), n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3.

[0899] Examples of the compound represented by formula (H6) include the following compounds.

[0900] [Chemical Formula 71]

[0901]

[0902] Examples of the hydroxy compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone and 2,3,4,3',4',5'-hexahydroxybenzophenone,

[0903] 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyvalerophenone, 2,3,4-trihydroxyhexanophenone and other polyhydroxyphenyl alkyl ketones,

[0904] Bis((poly)hydroxyphenyl)alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl)propane-1, nordihydroguaiaretic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane,

[0905] Polyhydroxybenzoates such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate,

[0906] Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)-methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-trihydroxybenzoyl)benzene and other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls,

[0907] Alkylene-bis(polyhydroxybenzoates) such as ethylene glycol-bis(3,5-dihydroxybenzoate) and ethylene glycol-bis(3,4,5-trihydroxybenzoate),

[0908] 2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3',5'-biphenyltetraol, 2,4,2',4'-biphenyltetraol, 2,4,6,3',5'-biphenylpentaol, 2,4,6,2',4',6'-biphenylhexanol, 2,3,4,2',3',4'-biphenylhexanol and other polyhydroxy biphenyls,

[0909] 4,4'-thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides,

[0910] 2,2',4,4'-tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers,

[0911] 2,2',4,4'-tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl) sulfoxides,

[0912] 2,2',4,4'-diphenylsulfone and other bis(polyhydroxyphenyl)sulfones,

[0913] tris(4-hydroxyphenyl)methane, 4,4',4''-trihydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',3'',4''-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4'-(3,4-diol-benzylidene)bis[2,6-dimethylphenol], 4,4'-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4',2",3'',4"-pentahydroxy-3,5 , 3',5'-tetramethyltriphenylmethane, 2,3,4,2',3',4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2',3',4',3",4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane and other polyhydroxytriphenylmethanes, 4,4'-(phenylmethylene)bisphenol, 4,4'-(1-phenyl-ethylidene)bis[2-methylphenol], 4,4',4"-ethylidene-triphenol and other polyhydroxytriphenylethanes,

[0914] 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-5,6,5',6'-tetrol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-5,6,7,5',6',7'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-4,5,6,4',5',6'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-4,5,6,5',6',7'-hexol and other polyhydroxy spirobis-indanes, 2,4,4-trimethyl-2',4',7'-trihydroxyflavan and other polyhydroxyflavans,

[0915] Polyhydroxyphthalides such as 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3',4',5',6'-tetrahydroxybis[phthalide-3,9'-xanthen], flavonoid pigments such as morin, quercetin, and rutin,

[0916] α,α',α''-tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-diisopropyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3-methyl- 4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α',α"-tris(3-methoxy-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α''-tris(2,4-dihydroxyphenyl)1,3,5-triisopropylbenzene, 1,3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxyphenylthiomethyl)mesitylene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4'-hydroxyphenyl)ethyl]-3- [α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(3",5"-dimethyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methoxy-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4-[ Polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 4-253058, such as α',α'-bis(4''-hydroxyphenyl)ethyl]benzene and 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene; polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 5-224410, such as α,α,α',α',α",α"-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene; poly(hydroxyphenyl)alkanes described in Japanese Patent Application Laid-Open No. 5-303200 and EP-530148, such as 1,2,2,3-tetra(p-hydroxyphenyl)propane and 1,3,3,5-tetra(p-hydroxyphenyl)pentane;

[0917] p-Bis(2,3,4-trihydroxybenzoyl)benzene, p-Bis(2,4,6-trihydroxybenzoyl)benzene, m-Bis(2,3,4-trihydroxybenzoyl)benzene, m-Bis(2,4,6-trihydroxybenzoyl)benzene, p-Bis(2,5-dihydroxy-3-bromobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-nitrobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5 -cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-tetrakis(2,3,4-trihydroxybenzoyl)benzene, α,α'-bis(2,3,4-trihydroxybenzoyl)p-xylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl)mesitylene,

[0918] 2,6-bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis-(2-hydroxy-5'-methylbenzyl)-p-cresol, 2,6-bis-(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-bis-(4-hydroxy-3,5-dimethylbenzyl)-pyrogallol, 2,6-bis-( 4-hydroxy-3,5-dimethylbenzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethyl-phenol, 4,6-bis-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-phenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol, 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy -3,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2',6,6'-tetrakis[(4-hydroxyphenyl)methyl]-4,4'-methylenediphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, bis(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, 2,2'-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]6,6'-dimethyl-4,4'-methylenediphenol, 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobis(1H-indene)-5,5',6,6',7,7'hexanol, bis(4-hydroxy-3,5-dimethylphenyl)methyl]-(4-hydroxy-3-methoxyphenyl)methane, and the like.

[0919] Furthermore, low-nuclear forms of phenol resins such as novolac resins can also be used.

[0920] Examples of the naphthoquinonediazidesulfonic acid include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and these may be used in combination.

[0921] The method for producing naphthoquinonediazidesulfonic acid esters of hydroxy compounds is not particularly limited, and for example, naphthoquinonediazidesulfonic acid is sulfonylchlorinated with chlorosulfonic acid or thionyl chloride, and the obtained naphthoquinonediazidesulfonic acid chloride is subjected to a condensation reaction with a hydroxy compound.

[0922] For example, it can be obtained by reacting a hydroxy compound with a predetermined amount of naphthoquinonediazidesulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and then washing the obtained product with water and drying.

[0923] The esterification rate of naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or higher, more preferably 20% or higher. The upper limit of the esterification rate is not particularly limited and may be 100%.

[0924] The above esterification rate can be expressed as the ratio of esterified groups in the hydroxyl groups of the hydroxyl compound. 1 Confirmed by H-NMR etc.

[0925] Furthermore, as the light absorber, the compounds described in paragraphs 0088 to 0108 of JP-A-2019-206689 can also be used.

[0926] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and further preferably 1 to 5 mass %.

[0927] In particular, from the viewpoint of improving adhesion to a substrate, the resin composition of the present invention preferably further contains the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, it is easy to maintain adhesion to the substrate even after the cured product is exposed under particularly high temperature and high humidity conditions.

[0928] <Polymerization Inhibitor>

[0929] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0930] Specific examples of polymerization inhibitors include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenoxazine, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide. This information is incorporated herein.

[0931] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass based on the total solid content of the resin composition.

[0932] The polymerization inhibitor may be one or two or more. When two or more polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0933] <Other additives>

[0934] Resin combination of the present invention can contain various additives as needed in the scope of obtaining the effect of the present invention, for example, surfactant, higher fatty acid derivative, thermal polymerization initiator, inorganic particles, ultraviolet light absorber, organic titanium compound, antioxidant, light acid generator, polymerization inhibitor, phenolic compound, other macromolecular compounds, plasticizer and other auxiliary agents (for example, defoamer, flame retardant etc.) etc. By suitably containing these components, it is possible to adjust the properties such as film physical properties. About these components, for example, it is possible to refer to the record of (paragraph 0237 of corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification sheet) after 0183 paragraphs of Japanese Unexamined Patent Application Publication No. 2008-250074 publication, the record of paragraphs 0101~0104,0107~0109 etc., these contents are incorporated in this specification sheets. When blending these additives, it is preferably set to below the 3 mass % of the solids component of resin combination of the present invention by its total content.

[0935] 〔Surfactant〕

[0936] The resin composition preferably contains a surfactant from the viewpoint of exhibiting leveling properties during drying, suppressing coating film defects, and improving flatness.

[0937] As the surfactant, various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0938] Among these, compounds containing a silicon atom are preferred, and silicone-based surfactants are more preferred.

[0939] The inclusion of a surfactant in the photosensitive resin composition of the present invention can further enhance the liquid properties (particularly fluidity) when preparing the coating liquid composition, and can further improve the uniformity of the coating thickness and the efficiency of liquid conservation. Specifically, when a coating liquid containing a surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving wettability and coating properties. Consequently, a uniform film with minimal thickness variations can be formed.

[0940] Examples of the fluorine-based surfactant include compounds described in paragraph 0328 of International Publication No. 2021 / 112189, the contents of which are incorporated into this specification.

[0941] As a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used. The fluorine-containing polymer compound contains: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy). For example, the following compounds can be mentioned.

[0942] [Chemical Formula 72]

[0943]

[0944] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0945] Fluoropolymers having ethylenically unsaturated groups in their side chains can also be used as fluorochemical surfactants. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP-A-2010-164965, which are incorporated herein by reference. Commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0946] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in achieving uniform thickness of the coating film and saving liquid, and also have good solubility in the composition.

[0947] Examples of the silicone surfactant, hydrocarbon surfactant, nonionic surfactant, cationic surfactant, and anionic surfactant include compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189, the contents of which are incorporated into this specification.

[0948] The surfactant may be used alone or in combination of two or more.

[0949] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0950] [Higher fatty acid derivatives]

[0951] In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so that it is localized on the surface of the resin composition during the drying process after coating.

[0952] Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used, and the contents thereof are incorporated into the present specification.

[0953] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The higher fatty acid derivative may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, their total is preferably within the above range.

[0954] [Thermal polymerization initiator]

[0955] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy and initiate or promote the polymerization reaction of polymerizable compounds. Adding a thermal free radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. Furthermore, photopolymerization initiators sometimes also have the function of initiating polymerization through heat and can sometimes be added as thermal polymerization initiators.

[0956] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.

[0957] When the resin composition contains a thermal polymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass relative to the total solid content of the resin composition. The thermal polymerization initiator may be contained in one type or in two or more types. When containing two or more types of thermal polymerization initiators, the total amount is preferably within the above range.

[0958] 〔Inorganic particles〕

[0959] Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0960] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0961] The average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using, for example, Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0962] When the above measurement is difficult to perform, measurement can also be performed by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0963] [Ultraviolet absorber]

[0964] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.

[0965] Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of International Publication No. 2021 / 112189, the contents of which are incorporated into the present specification.

[0966] The ultraviolet absorbers may be used alone or in combination of two or more.

[0967] When the resin composition contains a UV absorber, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, based on the total solid content of the resin composition.

[0968] [Organic titanium compounds]

[0969] Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0970] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0971] Specific examples of the organic titanium compound are shown in the following I) to VII).

[0972] 1) Titanium chelate compound: From the perspective of excellent storage stability of the resin composition and the ability to obtain a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples include titanium diisopropylate bis(triethanolamine), titanium diisopropylate bis(2,4-pentanedione), titanium diisopropylate bis(2,4-pentanedione), titanium diisopropylate bis(tetramethylheptanedione), titanium diisopropylate bis(ethyl acetoacetate), and the like.

[0973] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, and titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0974] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0975] IV) Monoalkoxy titanium compounds: Examples include tris(dioctylphosphate)titanium isopropoxide and tris(dodecylbenzenesulfonate)titanium isopropoxide.

[0976] V) Titanium oxide compound: Examples include bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, and titanium phthalocyanine oxide.

[0977] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0978] VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate.

[0979] Among these, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of achieving better chemical resistance. In particular, bis(ethyl acetoacetate)titanium diisopropylate, tetra(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0980] Furthermore, it is preferable to contain a compound represented by the following formula (T-1) as the organic titanium compound or in place of the organic titanium compound.

[0981] [Chemical Formula 73]

[0982]

[0983] In formula (T-1), M is titanium, zirconium or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1+l2×2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1+l2+m+n×2=4, R 11 are each independently a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted alkoxy, or a substituted or unsubstituted phenoxy, R 12is a substituted or unsubstituted hydrocarbon group, R 2 Each independently represents a group containing a structure represented by the following formula (T-2), R 3 Each independently represents a group containing a structure represented by the following formula (T-2), X A are each independently an oxygen atom or a sulfur atom.

[0984] [Chemical Formula 74]

[0985]

[0986] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, * represents a bonding site with other structures, and # represents a bonding site with a metal atom.

[0987] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium.

[0988] In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention.

[0989] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0990] In formula (T-1), n ​​is preferably 1 or 2, more preferably 1.

[0991] Among them, in formula (T-1), preferably, 11 and 12 are 0, and m is 0, 2 or 4.

[0992] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R 11 Substituted or unsubstituted cyclopentadienyl ligands are preferred.

[0993] And, R 11 The cyclopentadienyl, alkoxy and phenoxy groups in the group may be substituted, but an unsubstituted form is also a preferred form of the present invention.

[0994] In formula (T-1), R 12 It is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.

[0995] As R 12 The hydrocarbon group in may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and is preferably an aromatic hydrocarbon group.

[0996] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0997] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably a phenylene group.

[0998] As R 12 The substituent in is preferably a monovalent substituent, and examples thereof include a halogen atom. 12 When it is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.

[0999] Among these, in formula (T-1), R 12 Preferably, it is an unsubstituted phenylene group. 12 The phenylene group in is preferably 1,2-phenylene.

[1000] In formula (T-1), m is 2 or more, when it contains 2 or more R 2 When the two or more R 2 The structures of can be the same or different.

[1001] In formula (T-1), n ​​is 2 or more, when it contains 2 or more R 3 When the two or more R 3 The structures of can be the same or different.

[1002] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[1003] Specific examples of the compound represented by formula (T-1) include compounds corresponding to I-5 to I-8 in Examples, but are not limited thereto.

[1004] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or greater, the heat resistance and drug resistance of the resulting cured pattern are further improved, while when the content is 10 parts by mass or less, the storage stability of the composition is further improved.

[1005] [Antioxidant]

[1006] By including an antioxidant as an additive, the elongation characteristics of the cured film or the adhesion to the metal material can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189, which are incorporated into this specification.

[1007] The antioxidant content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting the added amount to 0.1 parts by mass or greater, it is easier to achieve improved elongation properties and adhesion to metal materials, even in high-temperature and high-humidity environments. Furthermore, by setting the added amount to 10 parts by mass or less, the sensitivity of the resin composition can be increased, for example, through interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, their combined amount is preferably within the above-mentioned range.

[1008] 〔Polymerization inhibitor〕

[1009] Examples of the polymerization inhibitor include sodium polyacrylate and the like.

[1010] The polymerization inhibitor may be used alone or in combination of two or more.

[1011] When the resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, based on the total solid content of the resin composition.

[1012] (Phenolic compounds)

[1013] Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (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 YUKIZAICORPORATION), and the like.

[1014] The phenolic compounds may be used alone or in combination of two or more.

[1015] When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, based on the total solid content of the resin composition.

[1016] 〔Other polymer compounds〕

[1017] Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

[1018] The other polymer compounds may be used alone or in combination of two or more.

[1019] When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass to 30% by mass, more preferably 0.02% by mass to 20% by mass, based on the total solid content of the resin composition.

[1020] <Characteristics of Resin Composition>

[1021] The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000mm 2 / s~10,000mm 2 / s, more preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000mm 2 / s or more, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000 mm 2 / s or less, a coating film with excellent coating surface shape can be obtained.

[1022] <Regarding Restrictions on Substances Contained in the Resin Composition>

[1023] The resin composition of the present invention preferably has a water content of less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. When the water content is less than 2.0%, the storage stability of the resin composition is improved.

[1024] Examples of methods for maintaining the moisture content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[1025] From the perspective of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, excluding metals contained in complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[1026] In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention; lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that minimize contamination.

[1027] Regarding the resin composition of the present invention, when considering its use as a semiconductor material, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the perspective of wiring corrosion resistance. Among them, the halogen atoms present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is preferably within the above-mentioned ranges.

[1028] As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

[1029] Conventionally known containers can be used as containers for the resin composition of the present invention. In order to suppress the incorporation of impurities into the raw materials or the resin composition of the present invention, multilayer bottles having an inner wall composed of six layers of six different resins or bottles having a seven-layer structure composed of six different resins are also preferably used as containers. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[1030] <Cured Product of Resin Composition>

[1031] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1032] The cured product of the present invention is a cured product obtained by curing the resin composition.

[1033] The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and a film-like, rod-like, spherical, granular, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[1034] The shrinkage during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. The shrinkage refers to the percentage of volume change before and after curing of the resin composition and can be calculated using the following formula.

[1035] Shrinkage [%] = 100 - (volume after curing ÷ volume before curing) × 100

[1036] <Characteristics of Cured Resin Composition>

[1037] The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or higher, the cured product may have excellent mechanical properties.

[1038] The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[1039] The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[1040] <Preparation of Resin Composition>

[1041] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by a conventionally known method.

[1042] Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing while rotating a pot.

[1043] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[1044] For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to perform filtration using a filter. Regarding the filter pore size, for example, it is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and further 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, HDPE (high-density polyethylene) is more preferred. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage in series can be cited. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be a circulation filtration. In addition, filtration can also be performed after pressurization. When filtering is performed after pressurization, the applied pressure is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, further preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa.

[1045] In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filter filtration and impurity removal using an adsorbent can also be combined. Known adsorbents can be used as adsorbents. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[1046] After filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[1047] (Method for producing cured product)

[1048] The first embodiment of the method for producing a cured product of the present invention (hereinafter also referred to as "the first method for producing a cured product") preferably includes a film-forming step of applying the resin composition to a substrate to form a film.

[1049] The method for producing the first cured product preferably includes a drying step after the film forming step.

[1050] The method for producing the first cured product more preferably includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed in the film forming step (or the film after the drying step as needed), and a developing step of developing the film exposed in the exposure step using a developer to form a pattern.

[1051] The method for producing the first cured product particularly preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step.

[1052] Furthermore, the method for producing the first cured product preferably also includes the film forming step and the step of heating the film.

[1053] Hereinafter, the details of each step will be described.

[1054] <Film Formation Step>

[1055] The resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film.

[1056] The method for producing the first cured product of the present invention preferably includes a film-forming step of applying the resin composition on a substrate to form a film.

[1057] 〔Base material〕

[1058] The type of substrate can be appropriately determined according to the application and is not particularly limited. As the substrate, there can be mentioned semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, any one of a substrate formed of a metal and a substrate having a metal layer formed by, for example, plating, vapor deposition, etc.), paper, SOG (Spin On Glass: spin-on glass), TFT (thin film transistor) array substrates, mold substrates, electrode plates of plasma display panels (PDPs), etc. In particular, the substrate is preferably a semiconductor manufacturing substrate, more preferably a silicon substrate, a Cu substrate, and a mold substrate.

[1059] On the surface of these substrates, a layer such as an adhesive layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided.

[1060] The shape of the substrate is not particularly limited and may be circular or rectangular.

[1061] Regarding the size of the substrate, for example, if the substrate is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm, and for example, if the substrate is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.

[1062] As the substrate, for example, a plate-shaped substrate (substrate) can be used, and preferably a panel-shaped substrate (base plate) is used.

[1063] When a film is formed by applying the resin composition on the surface of a resin layer (for example, a layer composed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a base material.

[1064] As a method of applying the resin composition to a substrate, coating is preferred.

[1065] As the method applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet method etc. can be cited. From the viewpoint of uniformity of film thickness, preferably spin coating, slit coating, spray coating or inkjet method, from the viewpoint of uniformity of film thickness and the viewpoint of productivity, more preferably spin coating and slit coating method. According to the method applied, the solid content concentration or coating conditions of the resin composition are adjusted, thereby a film of desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, preferably spin coating or spray coating, inkjet method etc., if it is a rectangular substrate, preferably slit coating, spray coating, inkjet method etc. In the case of spin coating, for example, it is possible to apply for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.

[1066] Furthermore, a method of transferring a coating film formed on a temporary support body in advance by the above-mentioned applying method to a substrate can also be applied.

[1067] As the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[1068] Furthermore, a process of removing excess film from the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backwash.

[1069] A pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[1070] <Drying Process>

[1071] After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

[1072] That is, the method for producing the first cured product of the present invention may include a drying step of drying the film formed in the film forming step.

[1073] The drying step is preferably performed after the film forming step and before the exposure step.

[1074] The film drying temperature in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Drying can also be performed under reduced pressure. The drying time can be, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[1075] Furthermore, the drying step preferably satisfies either of the following conditions i and ii.

[1076] Condition i: The heating temperature in the drying step is 120°C or higher and lower than 150°C.

[1077] Condition ii: The heating temperature in the drying step is lower than 120° C. and the heating time is 5 minutes or longer.

[1078] It is presumed that by satisfying at least one of conditions i and ii, the solvent can be removed and curing during drying can be suppressed, so that reflow of the resin layer in the heating step becomes easy and a film having excellent flatness can be obtained.

[1079] When the drying step is performed under condition i, the drying temperature is preferably 120 to 140°C, more preferably 120 to 130°C.

[1080] When the drying step is performed under condition i, the drying time is preferably 1 to 10 minutes, more preferably 2 to 5 minutes.

[1081] When the drying step is performed under condition i, the drying may be performed under atmospheric pressure or under reduced pressure.

[1082] The drying mechanism when the drying step is performed under condition i is not particularly limited, but a hot plate can be used, for example.

[1083] When the drying step is performed under condition ii, the drying temperature is preferably 90 to 115°C, more preferably 100 to 115°C.

[1084] When the drying step is performed under condition ii, the drying time is preferably 5 to 15 minutes, more preferably 5 to 10 minutes.

[1085] When the drying step is performed under condition ii, the drying may be performed under atmospheric pressure or under reduced pressure.

[1086] The drying mechanism when the drying step is performed under condition ii is not particularly limited, but a hot plate can be used, for example.

[1087] <Exposure Process>

[1088] The film can be subjected to an exposure step of selectively exposing the film.

[1089] The method for producing the first cured product may include an exposure step of selectively exposing the film formed in the film forming step.

[1090] Selective exposure refers to exposing a portion of the film to light, and selective exposure forms exposed areas (exposed areas) and unexposed areas (non-exposed areas) on the film.

[1091] The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably 200 to 8,000 mJ / cm 2 .

[1092] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[1093] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, and 355 nm), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), and wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, and (7) second harmonics of YAG lasers at 532 nm and third harmonics at 355 nm. For the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-rays is more preferred from the viewpoint of exposure sensitivity.

[1094] The exposure method is not particularly limited as long as at least a portion of the film composed of the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[1095] <Post-exposure heating process>

[1096] The film may be subjected to a step of heating after exposure (post-exposure heating step).

[1097] That is, the method for producing the first cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

[1098] The post-exposure heating step can be performed after the exposure step and before the development step.

[1099] The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[1100] The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1101] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature.

[1102] Furthermore, the heating rate can be appropriately changed during the heating process.

[1103] The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[1104] Furthermore, heating is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[1105] <Development Process>

[1106] The film after exposure can be subjected to a development step of developing with a developer to form a pattern.

[1107] That is, the method for producing the first cured product of the present invention may include a developing step of developing the film exposed in the exposure step using a developing solution to form a pattern.

[1108] By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

[1109] Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[1110] 〔Developer〕

[1111] As a developer used in the development step, an aqueous alkaline solution or a developer containing an organic solvent can be mentioned.

[1112] When the developer is an alkaline aqueous solution, examples of the alkaline compound that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass, based on the total amount of the developer.

[1113] When the developer contains an organic solvent, the compounds described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. Furthermore, preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[1114] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and particularly preferably containing cyclopentanone.

[1115] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. The above content may also be 100% by mass.

[1116] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. The at least one of the alkaline compound and the alkali generator in the developer may penetrate into the pattern, thereby sometimes improving properties such as elongation at break of the pattern.

[1117] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).

[1118] As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred.

[1119] As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is unlikely to remain in the cured film (the obtained cured product) is preferred. From the viewpoint of promoting cyclization, a compound whose residual amount is unlikely to be reduced by vaporization or the like before heating is preferred.

[1120] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101, 325 Pa).

[1121] The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[1122] For example, when the boiling point of the organic solvent is 100°C, the base used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.

[1123] The developer may contain only one basic compound or two or more basic compounds.

[1124] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butylenediamine, 1,5-diaminopentane, and N-methylhexylamine. , N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

[1125] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[1126] When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[1127] When the basic compound or base generator is solid in an environment where a developer is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the developer.

[1128] The developer may contain only one or more of the alkaline compound and the alkali generator. When the alkaline compound and the alkali generator are two or more, the total amount thereof is preferably within the above range.

[1129] The developer may further contain other components.

[1130] Examples of other components include known surfactants and known defoaming agents.

[1131] [Developer Supply Method]

[1132] The method for supplying the developer is not particularly limited as long as the desired pattern can be formed. Examples include immersing the film-formed substrate in the developer, using a nozzle to supply the developer to the film formed on the substrate using a rotary immersion development method, and continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

[1133] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or continuously supply it using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply it using a spray nozzle.

[1134] In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[1135] Examples of methods for supplying the developer in the development step include continuously supplying the developer to the substrate, maintaining the developer substantially stationary on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof.

[1136] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10°C to 45°C, more preferably 18°C ​​to 30°C.

[1137] In the development step, the pattern may be cleaned (rinsed) with a rinse solution after the development with the developer. Alternatively, a method may be employed in which the rinse solution is supplied before the developer in contact with the pattern completely dries.

[1138] [Rinse solution]

[1139] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse liquid. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[1140] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as exemplified when the developer contains an organic solvent.

[1141] The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility of the pattern than the organic solvent contained in the developer.

[1142] When the rinse liquid contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[1143] When the rinsing liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more relative to the total mass of the rinsing liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinsing liquid.

[1144] The flushing liquid may contain at least one of a basic compound and an alkali generator.

[1145] Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, an alkaline compound, and an alkali generator is also one of the preferred embodiments of the present invention.

[1146] Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generators that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same.

[1147] The basic compound and base generator contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.

[1148] When the rinse liquid contains at least one of a basic compound and an alkali generator, the content of the basic compound or alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[1149] When the basic compound or base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the rinse liquid.

[1150] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one of the at least one of the alkaline compound and the alkali generator, or may contain two or more of the at least one of the alkaline compound and the alkali generator. When there are two or more of the at least one of the alkaline compound and the alkali generator, the total amount of the at least one of the alkaline compound and the alkali generator is preferably within the above range.

[1151] The rinse may also contain other ingredients.

[1152] Examples of other components include known surfactants and known defoaming agents.

[1153] [How to supply flushing fluid]

[1154] As long as the desired pattern can be formed, there is no particular restriction on the method of supplying the rinsing liquid. The following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through liquid accumulation, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through means such as a straight nozzle.

[1155] From the perspectives of the permeability of the rinse liquid, the removal of the non-image area, and manufacturing efficiency, there are methods for supplying the rinse liquid using shower nozzles, straight nozzles, spray nozzles, etc. Continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, supply using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

[1156] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[1157] As a method for supplying the rinsing liquid in the rinsing step, a process of continuously supplying the rinsing liquid to the substrate, a process of maintaining the rinsing liquid in a roughly static state on the substrate, a process of vibrating the rinsing liquid on the substrate using ultrasound, etc., and a combination of these processes can be adopted.

[1158] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10°C to 45°C, more preferably 18°C ​​to 30°C.

[1159] In the development process, after processing with a developer or cleaning the pattern with a rinse solution, a process of bringing the treatment liquid into contact with the pattern may be included. Alternatively, a method of supplying the treatment liquid before the developer or rinse solution in contact with the pattern has completely dried may be adopted.

[1160] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator.

[1161] Preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator used in the rinse solution.

[1162] The method of supplying the processing liquid to the pattern can be the same method as the method of supplying the rinse liquid described above, and the preferred aspects are also the same.

[1163] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1164] Furthermore, when the basic compound or base generator is solid in the environment where the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass relative to the total solid content of the treatment liquid.

[1165] When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one of the at least one of the alkaline compound and the alkali generator, or may contain two or more of the at least one of the alkaline compound and the alkali generator. When there are two or more of the at least one of the alkaline compound and the alkali generator, the total amount of the at least one of the alkaline compound and the alkali generator is preferably within the above range.

[1166] <Heating process>

[1167] The pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development.

[1168] That is, the method for producing the first cured product of the present invention may include a heating step of heating the pattern obtained in the development step.

[1169] Furthermore, the method for producing a first cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the development step or a film obtained by the film formation step.

[1170] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide.

[1171] Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or a crosslinking agent other than the specific resin is also performed.

[1172] The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, and...

Claims

1. A resin composition containing at least one resin selected from polyimide and its precursors, wherein the dielectric loss tangent of the cured product obtained by heating the resin composition at 230 °C for 1 hour is less than 0.

03.

2. A resin composition containing at least one resin selected from polyimide and its precursors, wherein the dielectric loss tangent of the resin is less than 0.

025.

3. The resin composition according to claim 1 or 2, further containing a polymerizable compound and a photoinitiator.

4. The resin composition according to claim 3, wherein, the polymerizable compound contains an acryloyl group.

5. The resin composition according to claim 1 or 2, wherein, the weight average molecular weight of the resin is 20,000 or less.

6. The resin composition according to claim 1 or 2, wherein, the resin has a polymerizable group.

7. The resin composition according to claim 1 or 2, wherein, the resin has a vinylphenyl group.

8. The resin composition according to claim 1 or 2, wherein, the resin has a group formed by removing two or more hydrogen atoms from the structure represented by the following formula (A-1), In formula (A-1), A 1 ~A 3 are each independently a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) each optionally have a substituent.

9. The resin composition according to claim 1 or 2, further containing a solvent having a boiling point of 180 °C or less.

10. The resin composition according to claim 9, further containing a solvent having a boiling point exceeding 180 °C.

11. The resin composition according to claim 1 or 2, further containing a surfactant.

12. The resin composition according to claim 11, wherein, the surfactant is a compound containing a silicon atom.

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

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

15. A laminate comprising two or more layers made of the cured product according to claim 14, and containing a metal layer between any layers of the layers made of the cured product.

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

17. A method for manufacturing a cured product, which comprises: a drying step of heating and drying a resin composition containing at least one resin selected from polyimide and its precursors and having a dielectric loss tangent of the resin less than 0.025 to form a film; a heating step of heating the film, wherein the method for manufacturing the cured product satisfies any one of the following conditions i to v, Condition i: The heating temperature in the drying step is 120 °C or more and less than 150 °C, Condition ii: The heating temperature in the drying step is less than 120 °C and the heating time is 5 minutes or more, Condition iii: The heating temperature in the heating step is 240 °C or more, Condition iv: The heating temperature in the heating step is 150 °C or more and less than 240 °C and the heating time is 3 hours or more, Condition v: The heating process includes at least a first heating process and a second heating process carried out after the first heating process. The heating temperature in the first heating process is 150°C or higher and less than 200°C, and the heating temperature in the second heating process is 200°C or higher.

18. A method for manufacturing a cured product, which comprises: a drying process of heating and drying a curable composition containing at least one resin selected from polyimide and its precursors to form a film; a heating process of heating the film, and the tangent of the dielectric loss angle of the obtained cured product is less than 0.03, the method for manufacturing the cured product satisfies any one of the following conditions i to condition v, Condition i: The heating temperature in the drying process is 120°C or higher and less than 150°C, Condition ii: The heating temperature in the drying process is less than 120°C and the heating time is 5 minutes or longer, Condition iii: The heating temperature in the heating process is 240°C or higher, Condition iv: The heating temperature in the heating process is 150°C or higher and less than 240°C and the heating time is 3 hours or longer, Condition v: The heating process includes at least a first heating process and a second heating process carried out after the first heating process. The heating temperature in the first heating process is 150°C or higher and less than 200°C, and the heating temperature in the second heating process is 200°C or higher.

19. The method for manufacturing a cured product according to claim 17 or 18, wherein, between the drying process and the heating process, it includes an exposure process of selectively exposing the film and a developing process of developing the film with a developer to form a pattern.

20. A method for manufacturing a laminate, which includes the method for manufacturing a cured product according to claim 16.

21. A method for manufacturing a semiconductor device, which includes the method for manufacturing a cured product according to claim 16.

22. A semiconductor device, which contains the cured product according to claim 14.

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