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

Abstract

A resin composition, a cured product obtained by curing the composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product. The resin composition contains at least one resin selected from the group consisting of polyimides and precursors thereof, a polymerizable compound, and a polymerization initiator, and a film having a thickness of 10 [mu] m obtained from the resin composition has a dissolution rate of 0.01-0.55 [mu] m / sec with respect to cyclopentanone.

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, resin materials produced from resin compositions containing resins are used in a variety of fields.

[0003] For example, polyimide is suitable for a wide variety of applications due to its excellent heat resistance and insulation properties. These applications are not particularly limited, but, for example, using semiconductor devices for mounting, it can be used as an insulating film, a sealing material, or a protective film. Furthermore, it can be used as a base film or cover film 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 having a metal on at least a portion of its surface (hereinafter also referred to as a metal-containing substrate) by coating to form a photosensitive film, and then exposed, developed, heated, etc. as needed to form a cured product on the metal-containing 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 other methods, and therefore has excellent manufacturing adaptability. For example, the resin composition has a high degree of design freedom in terms of its shape, size, and application location. In addition to the high performance of polyimide, this excellent manufacturing adaptability is leading to increasing anticipation for the industrial application and development of the resin composition.

[0008] Furthermore, such resin materials are required to have excellent adhesion to metal-containing substrates, and various methods are being studied to improve the adhesion to metal-containing substrates.

[0009] For example, Patent Document 1 describes a photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a silicon compound having a secondary aromatic amino group and an alkoxy group, and (c) at least one selected from a photopolymerization initiator, a photoacid generator, and a photobase generator.

[0010] Previous technical literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2007 / 004345 Summary of the Invention

[0013] Technical issues to be solved by the invention

[0014] A resin composition containing a polyimide or a precursor thereof is required to provide a cured product having excellent adhesion to a metal-containing substrate over a long period of time (and after an accelerated test).

[0015] The object of the present invention is to provide a resin composition that can produce a cured product having excellent adhesion to a metal-containing substrate over a long period of time, a cured product formed by curing the above resin composition, a laminate containing the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the method for producing the above cured product, and a semiconductor device containing the above cured product.

[0016] Means for solving technical problems

[0017] Hereinafter, examples of representative embodiments of the present invention will be described.

[0018] <1> A resin composition comprising:

[0019] A resin selected from at least one of polyimide and a polyimide precursor having a cyclic imide structure; and

[0020] Compound A has at least one structure selected from a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure.

[0021] <2> according to <1> The resin composition further comprises a compound B represented by the following formula (B-1).

[0022] [Chemical Formula 1]

[0023]

[0024] In formula (B-1), R B1 Represents a tertiary alkyl group, R B2 Each independently represents a hydrogen atom or an organic group.

[0025] <3> according to <1> or <2> The resin composition, wherein

[0026] The total amount of the cyclic imide structure and the cyclic isomide structure in the polyimide precursor is 0.06 to 2.40 mmol / g.

[0027] <4> A resin composition comprising:

[0028] A resin selected from at least one of polyimide and a polyimide precursor;

[0029] Compound A having at least one structure selected from a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure; and

[0030] Compound B represented by the following formula (B-1).

[0031] [Chemical Formula 2]

[0032]

[0033] In formula (B-1), R B1 Represents a tertiary alkyl group, R B2 Each independently represents a hydrogen atom or an organic group.

[0034] <5> according to <1> to <4> The resin composition according to any one of the preceding claims, wherein

[0035] The compound A contains at least one compound selected from the group consisting of compounds represented by formula (A-1) and formula (A-2).

[0036] [Chemical Formula 3]

[0037]

[0038] In formula (A-1), R 1 Each independently represents a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is optionally substituted by a substituent, or an alkylthio group in which a hydrogen atom is optionally substituted by a substituent, and R 2 Each independently represents a hydrogen atom or an organic group, R 1 and R 2 At least two of them may be bonded to form a ring structure.

[0039] In formula (A-2), R 1 Each independently represents a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is optionally substituted by a substituent, or an alkylthio group in which a hydrogen atom is optionally substituted by a substituent, and R 2 Each independently represents a hydrogen atom or an organic group, R 1 and R 2 At least two of them may be bonded to form a ring structure.

[0040] <6> according to <1> to <5> The resin composition described in any one of the preceding claims further comprises a solvent having at least one of an amide bond and a hydroxyl group.

[0041] <7> according to <1> to <6> The resin composition described above further comprises a polymerization initiator and a sensitizer.

[0042] <8> according to <1> to <7> The resin composition described above further comprises a urea compound.

[0043] <9> according to <1> to <8> The resin composition described in any one of the preceding claims, further comprising a compound containing a Group IV element.

[0044] <10> according to <9> The resin composition, wherein

[0045] The compound containing a Group IV element is a compound containing a titanium atom.

[0046] <11> according to <10> The resin composition, wherein

[0047] The above-mentioned compound containing a titanium atom further includes an organic titanium complex.

[0048] <12> according to <1> to <11> The resin composition described in any one of the preceding claims is used for forming an interlayer insulating film for a redistribution layer.

[0049] <13> A solidified material, which is <1> to <12> The resin composition described above is cured.

[0050] <14> A laminate comprising two or more layers of <13> The layers are formed of the above-mentioned cured product, and a metal layer is included between any layers formed of the above-mentioned cured product.

[0051] <15> A method for producing a solidified product, comprising: <1> to <12> Any one of the resin compositions is preferably used in a film-forming step of forming a film on a substrate.

[0052] <16> according to <15> The method for manufacturing the solidified material comprises:

[0053] An exposure step of selectively exposing the film; and

[0054] In the development step, the film is developed using a developer to form a pattern.

[0055] <17> according to <15> or <16> The method for producing the cured product includes a heating step of heating the film at 50 to 450°C.

[0056] <18> A method for manufacturing a laminated body, comprising: <15> to <17> The method for producing a cured product according to any one of the above.

[0057] <19> A method for manufacturing a semiconductor device, comprising: <15> to <17> The method for producing a cured product according to any one of the above.

[0058] <20> A semiconductor device comprising <13> The solidified material.

[0059] Effects of the Invention

[0060] According to the present invention, there are provided a resin composition that can produce a cured product having excellent adhesion to a metal-containing substrate over a long period of time, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product. DETAILED DESCRIPTION

[0061] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0062] In this specification, the numerical range expressed using the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0063] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0064] In the description of groups (atomic groups) in this specification, the term "not indicating substituted 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).

[0065] 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 activating light or radiation.

[0066] In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either “acryloyl” and “methacryloyl”.

[0067] 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.

[0068] 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.

[0069] In this specification, as long as there is no special instructions, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION), protection column HZ-L, TSKgel Super HZM-M, TSKgel SuperHZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are connected in series and used as column, thus weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. As long as there is no special instructions, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, in the case where solubility is relatively low, in the case where THF is not suitable as eluent, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm was used for detection in GPC measurement.

[0070] 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, a third layer or element can be further interposed 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. As long as there is no special instructions, the direction of the substrate stacked layer will be referred to as " on ", or in the case of the presence of 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 such up and down directions is for the convenience of illustrating this specification, and in actual mode, the " up " direction in this specification is also likely to be different from the vertical upward direction.

[0071] In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component.

[0072] 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.

[0073] In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0074] (Resin composition)

[0075] The resin composition involved in the first embodiment of the present invention (hereinafter also referred to as the "first resin composition") includes: a resin selected from at least one of polyimide and a polyimide precursor having a cyclic imide structure; and a compound A having a structure selected from at least one of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure.

[0076] The resin composition involved in the second embodiment of the present invention (hereinafter also referred to as the "second resin composition") comprises: a resin selected from at least one of polyimide and a polyimide precursor; a compound A having a structure selected from at least one of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure; and a compound B represented by formula (B-1).

[0077] Hereinafter, the first resin composition and the second resin composition are also collectively referred to simply as "resin composition".

[0078] Hereinafter, at least one resin selected from the group consisting of polyimide and a polyimide precursor having a cyclic imide structure contained in the first resin composition is also referred to as a “first specific resin”.

[0079] Hereinafter, at least one resin selected from the group consisting of polyimide and polyimide precursor contained in the second resin composition is also referred to as a "second specific resin."

[0080] Hereinafter, when simply described as "specific resin", it refers to both the first specific resin and the second specific resin.

[0081] The resin composition of the present invention is preferably used to form a photosensitive film to be exposed to light and developed, and is preferably used to form a film to be exposed to light and developed using a developer containing an organic solvent.

[0082] 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.

[0083] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive-tone development, and can also be used to form a photosensitive film for negative-tone development.

[0084] In the present invention, negative-tone development refers to development in which unexposed portions are removed by development during exposure and development, and positive-tone development refers to development in which exposed portions are removed by development.

[0085] 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.

[0086] According to the resin composition of the present invention, a cured product having excellent adhesion to a metal-containing substrate over a long period of time can be obtained.

[0087] The mechanism by which the above effects are achieved is not yet clear, but is speculated as follows.

[0088] The resin composition of the present invention contains a compound A having at least one structure selected from a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure.

[0089] Compounds having a 1,3-dicarbonyl structure and compounds having a β-hydroxycarbonyl structure are known to coordinate with metals to form complexes. Therefore, it is believed that by adding Compound A to the composition, Compound A coordinates to the metal in the metal-containing substrate in the film. Therefore, it is believed that the cured product obtained from the resin composition of the present invention exhibits excellent substrate adhesion after a high-temperature storage test.

[0090] Furthermore, in the first aspect of the present invention, the composition includes: a resin selected from at least one type of a polyimide and a polyimide precursor having a cyclic imide structure; and compound A.

[0091] It is considered that since the polarity of the imide structure contained in these resins is high, the compound A having similarly high polarity is easily dispersed in the film in a nearly uniform state.

[0092] As a result, metal ions from the metal-containing substrate can be uniformly captured, and migration of metal ions from the metal-containing substrate to the cured product is presumably effectively suppressed.

[0093] The second embodiment of the present invention comprises compound A and compound B having a specific structure.

[0094] The antioxidant compound B can suppress oxidation of the metal-containing substrate surface. However, complete oxidation suppression is difficult, and it is believed that the metal-containing substrate is oxidized over time or during high-temperature storage tests of models over time, leading to metal ions migrating from the interface to the cured product.

[0095] Compound A captures metal ions that migrate from the metal-containing substrate to the cured product and effectively suppresses this migration. In other words, it is believed that the combined use of Compound A and Compound B effectively suppresses both metal surface oxidation and metal ion migration, resulting in excellent substrate adhesion after the high-temperature storage test.

[0096] As described above, the result that the substrate adhesion after the high-temperature storage test was excellent is considered to be able to significantly improve the insulation reliability of the cured film.

[0097] Here, Patent Document 1 does not describe the first resin composition and the second resin composition.

[0098] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0099] <Specific resin>

[0100] The second resin composition of the present invention contains at least one resin (second specific resin) selected from the group consisting of polyimide and a polyimide precursor.

[0101] The polyimide precursor is a resin that changes its chemical structure by external stimulation to become a polyimide, preferably a resin that changes its chemical structure by heat, and more preferably a resin that forms a polyimide by forming a ring structure by a ring-closure reaction by heat.

[0102] The resin composition preferably contains a polyimide precursor as the specific resin.

[0103] The first specific resin of the present invention includes at least one resin (first specific resin) selected from the group consisting of polyimide and a polyimide precursor having a cyclic imide structure.

[0104] Here, the polyimide contained as the first specific resin is the same as the polyimide in the second specific resin, and the preferred aspects are also the same.

[0105] The polyimide precursor included as the first specific resin has a cyclic imide structure.

[0106] Furthermore, the polyimide precursor contained as the second specific resin preferably has a cyclic imide structure.

[0107] The cyclic imide structure refers to a cyclic structure containing two carbon atoms and a nitrogen atom contained in an imide group (*-C(=O)N(-*)C(=O)-*, where * represents a bonding site to another structure) as ring atoms of the ring structure.

[0108] The cyclic imide structure is not particularly limited, but is preferably a 5-membered ring structure.

[0109] Furthermore, the cyclic imide structure is preferably included in the main chain of the polyimide precursor.

[0110] As the cyclic imide structure, a structure represented by the following formula (CI-1) is preferred.

[0111] [Chemical Formula 4]

[0112]

[0113] In formula (CI-1), a dotted bond represents a single bond or a double bond, and * represents a bonding site with another bond.

[0114] In formula (CI-1), the dotted bond is preferably a double bond. When the dotted bond is a single bond, the hydrogen atoms in the two carbon atoms bonded to * via the single bond may be substituted with a known substituent.

[0115] When the specific resin is a polyimide precursor, the polyimide precursor may include a cyclic isoimide structure.

[0116] The cyclic isoimide structure refers to a cyclic structure containing two carbon atoms and a nitrogen atom as ring atoms of the ring structure and included in an isoimide group (*-C(=O)OC(=N(-*))-*, where * represents a bonding site to another structure).

[0117] The cyclic isoimido structure is not particularly limited, but is preferably a 5-membered ring structure.

[0118] Furthermore, the cyclic isoimide structure is preferably included in the main chain of the polyimide precursor.

[0119] As the cyclic isimide structure, a structure represented by the following formula (CI-2) is preferred.

[0120] [Chemical Formula 5]

[0121]

[0122] In formula (CI-2), a dotted bond represents a single bond or a double bond, and * represents a bonding site with another bond.

[0123] In formula (CI-2), the dotted bond is preferably a double bond. When the dotted bond is a single bond, the hydrogen atoms in the two carbon atoms bonded to * via the single bond may be substituted with a known substituent.

[0124] The total amount of the cyclic imide structure and the cyclic isomide structure in the polyimide precursor is preferably 0.06 to 2.40 mmol / g, more preferably 0.08 to 2.35 mmol / g, and even more preferably 0.10 to 2.20 mmol / g.

[0125] It is believed that when the amount of the cyclic imide structure is within the above range, the polyimide precursor itself has excellent solubility in the solvent and compatibility with other components in the composition, and also has excellent compatibility with compound A. Therefore, compound A is easily dispersed in the film in a nearly uniform state, and a cured product with excellent adhesion to the metal-containing substrate can be obtained for a long time.

[0126] The amount of the cyclic imide structure in the polyimide precursor can be adjusted by, for example, partially ring-closing the amic acid structure or amic acid ester structure in the polyimide precursor.

[0127] Specifically, it can be adjusted by the method described in the Examples described later.

[0128] From the viewpoint of improving developability, the acid value of the polyimide is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, further preferably 25 mgKOH / g or less, still further preferably 20 mgKOH / g or less, particularly preferably 15 mgKOH / g or less, and most preferably 10 mgKOH / g or less.

[0129] The lower limit of the acid value is not particularly limited, and may be 0 mgKOH / g or more.

[0130] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0131] When the specific resin contains an acid group, the acid group preferably has a pKa of 0 to 10, and more preferably has a pKa of 3 to 8, from the viewpoint of achieving both storage stability and developability.

[0132] pKa is a value representing the equilibrium constant Ka by its negative common logarithm pKa, taking into account the dissociation reaction of releasing hydrogen ions from an acid. In this specification, pKa is assumed to be a calculated value based on ACD / ChemSketch (registered trademark) unless otherwise specified. pKa can be referred to The Chemical Society o f Values ​​published in "Chemical Handbook, Basic Edition, 5th Revised Edition" edited by Japan.

[0133] When the acid group is a polyacid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant.

[0134] When the specific resin contains an acid group, the specific resin preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group as the acid group, and more preferably contains a phenolic hydroxyl group.

[0135] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0136] 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.

[0137] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0138] 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.

[0139] 〔Polyimide precursor〕

[0140] The type of the polyimide precursor used in the present invention is not particularly limited, but it preferably contains a repeating unit represented by the following formula (2).

[0141] [Chemical Formula 6]

[0142]

[0143] 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.

[0144] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR z -, preferably an oxygen atom.

[0145] R z represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0146] R in formula (2) 111Represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms or groups consisting of a combination thereof, and more preferably groups containing aromatic groups having 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the linear or branched aliphatic groups may be substituted with groups containing heteroatoms, and the hydrocarbon groups of the ring atoms of the cyclic aliphatic groups and aromatic groups may be substituted with groups containing heteroatoms. As R in formula (2) 111 Examples of the group represented by -Ar- and -Ar-L-Ar- can be cited, and a group represented by -Ar-L-Ar- is preferred. 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. These preferred ranges are as described above.

[0147] 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.

[0148] 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. More preferred are 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 of the ring atoms in the cyclic aliphatic and aromatic groups may be substituted with groups containing heteroatoms. Examples of groups containing aromatic groups include the following.

[0149] [Chemical Formula 7]

[0150]

[0151] In the formula, A 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 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, -0-, -C(=0)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0152] In the formula, * represents the bonding site with other structures.

[0153] Specifically, the diamine includes 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane;

[0154] 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;

[0155] 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 alkane, 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 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-diaminoisopropylbenzene, 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-trifluoromethyl) At least one diamine selected from the group consisting of 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'-diaminoquaternaryl.

[0156] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] Formula (51)

[0161] [Chemical Formula 8]

[0162]

[0163] 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 site to a nitrogen atom in formula (2).

[0164] 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).

[0165] [Chemical Formula 9]

[0166]

[0167] 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 site to a nitrogen atom in formula (2).

[0168] 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.

[0169] And, R 111 Also preferably, it is a group represented by the following formula (71). 111 More preferred is a group represented by the following formula (72).

[0170] [Chemical Formula 10]

[0171]

[0172] In formula (71), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, * represents a bonding site to the nitrogen atom in formula (2), and the hydrogen atoms of the four benzene rings described in formula (71) may be substituted with a substituent.

[0173] 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.

[0174] In formula (72), * represents a bonding site to the nitrogen atom in formula (2).

[0175] In formula (71), 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-.

[0176] In particular, A 1 and A 3 Preferred is -O-.

[0177] In particular, A 2 It is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.

[0178] Among these, A 1 and A 3 For -O- and A 2 The embodiment of -C(CH3)2- is also one of the preferred embodiments of the present invention.

[0179] 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.

[0180] 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.

[0181] Examples of the substituents on the four benzene rings described in formula (71) include fluorine atoms and hydrocarbon groups having 1 to 10 carbon atoms in which hydrogen atoms are optionally substituted with fluorine atoms.

[0182] Furthermore, an embodiment in which all four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0183] And, R 111 Also preferably, it is a group represented by the following formula (81). 111 More preferred is a group represented by the following formula (82).

[0184] [Chemical Formula 11]

[0185]

[0186] In formula (81), A 1 and A 2 Each independently represents a single bond or a divalent linking group, * represents a bonding site to the nitrogen atom in formula (2), and the hydrogen atoms of the three benzene rings described in formula (81) are optionally substituted with a substituent.

[0187] In formula (82), * represents a bonding site to the nitrogen atom in formula (2).

[0188] In formula (81), A 1 and A 2 Each of them is independently preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group consisting of a combination of two or more of these. It is more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, or a group consisting of a combination of two or more of these. It is further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms or -O-, and is particularly preferably -C(CH3)2-.

[0189] 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).

[0190] In formula (5) or formula (6), * each independently represents a bonding site with another structure.

[0191] [Chemical Formula 12]

[0192]

[0193] In formula (5), R 112 It is a single bond or a divalent connecting 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-, -CO-, -S-, -SO2- and -NHCO-, and 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-, -CO-, -S- and -SO2-, further preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0194] And, R 115Also preferably, it is a group represented by the following formula (7). 115 More preferred is a group represented by the following formula (7-2).

[0195] [Chemical Formula 13]

[0196]

[0197] In formula (7), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, * represents a bonding site to the carbonyl group in formula (2), and the hydrogen atoms of the four benzene rings described in formula (7) may be substituted with a substituent.

[0198] In formula (7-2), * represents a bonding site to the carbonyl group in formula (2).

[0199] In formula (7), A 1 ~A 3 The preferred embodiment of the substituents in the benzene ring is the same as that of A in the above formula (7-1). 1 ~A 3 , and the preferred embodiments of the substituents in the benzene ring are the same.

[0200] About R 115 Specifically, the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride can be cited. 115 The structure may include only one type of tetracarboxylic dianhydride residue or two or more types.

[0201] It is preferable that tetracarboxylic dianhydride is represented by the following formula (O).

[0202] [Chemical Formula 14]

[0203]

[0204] In formula (O), R 115 Represents a tetravalent organic group. 115 The preferred range of R in formula (2) has the same meaning as 115 The meanings and preferred ranges are the same.

[0205] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-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 tetracarboxylic dianhydride, anhydride, 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 alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0206] 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.

[0207] In formula (2), R 111 and R 115 At least one of them may also have an OH group. More specifically, as R 111 , for example, residues of bisaminophenol derivatives.

[0208] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As a 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 them comprises more than two polymerizable groups. As a polymerizable group, it is a group that can undergo 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 hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be enumerated. As the free radical polymerizable group possessed by the polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0209] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferred are groups represented by the following formula (III).

[0210] [Chemical Formula 15]

[0211]

[0212] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0213] In formula (III), * represents a bonding site with other structures.

[0214] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group.

[0215] 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. More preferred are alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups. Still more preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups.

[0216] 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.

[0217] 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, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0218] 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, further preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0219] 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.

[0220] 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.

[0221] 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 composed of multiple ethyleneoxy groups and multiple propyleneoxy groups. Polyethyleneoxy groups or polypropyleneoxy groups are more preferred, and polyethyleneoxy groups are even more preferred. In the group composed of multiple ethyleneoxy groups and multiple propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred embodiments of the number of repetitions of the ethyleneoxy group and the like in these groups are as described above.

[0222] In formula (2), R 113 In the case of a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0223] 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 under the action of an acid to generate 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 or ketal groups are more preferred.

[0224] 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.

[0225] 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.

[0226] Furthermore, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0227] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferred that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further expanded.

[0228] Formula (2-A)

[0229] [Chemical Formula 16]

[0230]

[0231] 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.

[0232] 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. 112 The meaning of is the same as R in formula (5) 112 The meanings and preferred ranges are the same.

[0233] 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.

[0234] 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 all repeating units. The above 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 total content is not particularly limited, and all repeating units in the polyimide precursor except the terminal can be repeating units represented by formula (2).

[0235] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0236] 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 preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0237] In this specification, the molecular weight dispersion is a value calculated by dividing the weight average molecular weight by the number average molecular weight.

[0238] 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 calculated for the multiple polyimide precursors as a single resin be within the above ranges.

[0239] 〔Polyimide〕

[0240] 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.

[0241] 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 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.

[0242] 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.

[0243] -Fluorine atom-

[0244] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms.

[0245] 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.

[0246] The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less based on the total mass of the polyimide.

[0247] -Silicon atoms-

[0248] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has silicon atoms.

[0249] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 More preferably, R is included in the repeating unit represented by the formula (4) described later as an organo-modified (poly)siloxane structure described later. 131 middle.

[0250] 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.

[0251] The amount of silicon atoms is preferably 1% by mass or more, and preferably 20% by mass or less, based on the total mass of the polyimide.

[0252] -Ethylenically unsaturated bond-

[0253] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0254] 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.

[0255] The ethylenically unsaturated bond preferably has radical polymerizability.

[0256] 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 included in R 132 or R 131 middle.

[0257] 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 included in R 131 middle.

[0258] Examples of the group having an ethylenically unsaturated bond include groups directly bonded to an aromatic ring and having an optionally substituted vinyl group, 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).

[0259] [Chemical Formula 17]

[0260]

[0261] 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.

[0262] In formula (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)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, and particularly preferably 2 or 3. The number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group composed of a combination of two or more of these.

[0263] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof.

[0264] 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.

[0265] Among these, R 21 The 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).

[0266] [Chemical Formula 18]

[0267]

[0268] 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 site with other structures, and ● represents the bonding site with R in formula (IV). 21 The bonding site of the bonded oxygen atom.

[0269] 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 as 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.

[0270] In formula (R1), X is preferably an oxygen atom.

[0271] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

[0272] 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).

[0273] The structure represented by formula (R2) can be obtained by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0274] 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).

[0275] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0276] The amount of the ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g, relative to the total mass of the polyimide.

[0277] -Polymerizable groups other than groups having an ethylenically unsaturated bond-

[0278] The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.

[0279] 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.

[0280] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably, for example, R 131 .

[0281] The amount of the polymerizable groups other than the group having an 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.

[0282] -Polarity conversion group-

[0283] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and the R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same, and preferred embodiments are also the same.

[0284] The polarity conversion group is, for example, contained in R in the repeating unit represented by the formula (4) described below. 131 、R 132 , the end of polyimide, etc.

[0285] -Acid value-

[0286] When the polyimide is subjected to 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.

[0287] 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.

[0288] When the polyimide is subjected to development using a developer containing an organic solvent as a 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.

[0289] The acid value is measured by a known method, for example, by the method described in JIS K0070:1992.

[0290] As the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred.

[0291] pKa is a value representing the equilibrium constant Ka by its negative common logarithm pKa, taking into account the dissociation reaction of releasing hydrogen ions from an acid. In this specification, pKa is assumed to be a calculated value based on ACD / ChemSketch (registered trademark) unless otherwise specified. o f Values ​​published in "Chemical Handbook, Basic Edition, 5th Revised Edition" edited by Japan.

[0292] When the acid group is a polyacid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant.

[0293] 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.

[0294] -phenolic hydroxyl group-

[0295] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0296] The polyimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group at a side chain.

[0297] 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.

[0298] 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.

[0299] 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).

[0300] [Chemical Formula 19]

[0301]

[0302] In formula (4), R 131 Represents a divalent organic group, R 132 represents a tetravalent organic group.

[0303] 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 the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0304] Formula (4-1)

[0305] [Chemical Formula 20]

[0306]

[0307] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as those in formula (4).

[0308] Formula (4-2)

[0309] [Chemical Formula 21]

[0310]

[0311] In formula (4-2), 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 meanings as those in formula (4).

[0312] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and the above-mentioned crosslinkable group other than the group having an ethylenically unsaturated bond.

[0313] R 131 The divalent organic group includes the following: 111 The same groups have the same preferred range.

[0314] As R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in formula (2) of the polyimide precursor can be cited. 111 example.

[0315] 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 total in one molecule is more preferred. A diamine residue containing no aromatic ring is further preferred.

[0316] 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 product names, manufactured by Huntsman), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0317] R 132 Represents a tetravalent organic group. Examples of the tetravalent organic group include the following: 115 The same groups have the same preferred range.

[0318] For example, as R 115 The four linkers of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in formula (4) to form a condensed ring.

[0319] 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.

[0320] Also preferably in 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.

[0321] The polyimide also 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.

[0322] In order 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.

[0323] In order to improve the storage stability of the resin composition, it is preferred to cap the main chain ends of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or a monoactive ester compound. Among these, it is more preferred to use a monoamine. Preferred compounds of the monoamine 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.

[0324] -Imidization rate (ring closure rate)-

[0325] From the viewpoint of film strength, insulation properties, etc. 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.

[0326] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0327] The imidization ratio is measured, for example, by the following method.

[0328] The infrared absorption spectrum of polyimide was measured and the absorption peak at 1377 cm-1, which is derived from the imide structure, was determined. -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.

[0329] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0330] Polyimide may contain repeating units all of R 131 and R 132 The repeating unit represented by the above formula (4) may also contain R 131 and R 132 The combination of contains two or more different repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. As other types of repeating units, for example, the repeating units represented by the above formula (2) can be cited.

[0331] Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacyl chloride compound, or monoactive ester end-capping agent) with a diamine at low temperature, obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, obtaining a diester from tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid, and reacting the diester with a diamine (partially substituted with a monoamine end-capping agent), and obtaining a polyimide precursor using a known imidization reaction method, or stopping the imidization reaction midway to introduce a partial imide structure, and introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0332] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. A weight-average molecular weight of 5,000 or greater can improve the bending resistance of the cured film. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or greater is particularly preferred.

[0333] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0334] 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 preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0335] 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 calculated for the multiple polyimides as a single resin be within the above ranges.

[0336] [Method for producing polyimide precursor, etc.]

[0337] The polyimide precursor and the like are produced, for example, by the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated into this specification.

[0338] 〔content〕

[0339] 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.

[0340] 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.

[0341] The resin composition of the present invention also preferably contains at least two types of resins.

[0342] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, may contain two or more specific resins, and preferably contains two or more specific resins.

[0343] When the resin composition of the present invention contains two or more specific resins, for example, it is preferably a polyimide precursor and contains a structure derived from a dianhydride (R in the above formula (2) 115 ) Two or more different polyimide precursors.

[0344] <Other resins>

[0345] 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").

[0346] Examples of other resins include polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0347] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[0348] For example, by adding a (meth)acrylic resin to the resin composition instead of or in addition to the polymerizable compound described below, the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of polymerizable groups per 1 g of the resin is 1×10 -3 mol / g or more).

[0349] 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, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0350] When the resin composition of the present invention contains other resins, the content of the other resins 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 further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0351] As a preferred embodiment of the resin composition of the present invention, it is also possible to set the content of other resins to be low. 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, as long as it is 0% by mass or more.

[0352] 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.

[0353] <Compound A>

[0354] The resin composition of the present invention contains compound A.

[0355] Compound A has at least one structure selected from a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure.

[0356] Here, the 1,3-dicarbonyl structure refers to a structure represented by the following formula (DC-1), and the β-hydroxycarbonyl structure refers to a structure represented by the following formula (HC-1).

[0357] [Chemical Formula 22]

[0358]

[0359] In formula (DC-1) or formula (HC-1), * and # each represent a bonding site to another structure. Here, * is preferably a bonding site to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, # is preferably a bonding site to a hydrogen atom or a carbon atom.

[0360] Here, the structure represented by the above-mentioned (DC-1) may be an enol type as represented by the following formula (DC-2).

[0361] Furthermore, the structure represented by the above-mentioned (HC-1) may be an enol type as represented by the following formula (HC-2).

[0362] [Chemical Formula 23]

[0363]

[0364] In formula (DC-2) or formula (HC-2), * and # each represent a bonding site to another structure. * is preferably a bonding site to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, # is preferably a bonding site to a hydrogen atom or a carbon atom.

[0365] Compound A preferably does not contain any metal atoms in its structure. The metal atoms mentioned here do not include metalloid atoms such as silicon dioxide.

[0366] Furthermore, it is preferred that the compound A does not coordinate to a metal atom in the resin composition.

[0367] 〔Molecular weight〕

[0368] The molecular weight of compound A is preferably 1,000 or less, more preferably 100 to 500, even more preferably 100 to 400, particularly preferably 100 to 350, even more preferably 100 to 300, and even more preferably 100 to 250.

[0369] [Compounds represented by formula (A-1) and formula (A-2)]

[0370] Compound A preferably contains at least one compound selected from the group consisting of compounds represented by the following formula (A-1) and formula (A-2).

[0371] [Chemical Formula 24]

[0372]

[0373] In formula (A-1), R 1 Each independently represents a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is optionally substituted by a substituent, or an alkylthio group in which a hydrogen atom is optionally substituted by a substituent, and R 2 Each independently represents a hydrogen atom or an organic group, R 1 and R 2 At least two of them may be bonded to form a ring structure.

[0374] In formula (A-2), R 1 Each independently represents a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is optionally substituted by a substituent, or an alkylthio group in which a hydrogen atom is optionally substituted by a substituent, and R 2 Each independently represents a hydrogen atom or an organic group, R 1 and R 2 At least two of them may be bonded to form a ring structure.

[0375] In formula (A-1), R 1 Preferably, each independently is a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, or an amino group in which a hydrogen atom is optionally substituted by a substituent, and more preferably a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, or an alkoxy group in which a hydrogen atom is optionally substituted by a substituent.

[0376] R 1 In the case of a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.

[0377] The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 1 or 2. The preferred range of the number of carbon atoms is the same as that of the aliphatic hydrocarbon group and the alkyl group.

[0378] Examples of the substituent in the hydrocarbon group in which the hydrogen atom is optionally substituted by a substituent include an alkoxy group, an alkoxycarbonyl group, an amino group in which the hydrogen atom is optionally substituted by a substituent, and a trialkoxysilyl group.

[0379] And, R 1 An embodiment in which the group is an unsubstituted hydrocarbon group is also one of the preferred embodiments of the present invention.

[0380] R 1 In the case of an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, the number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 1 or 2.

[0381] Examples of the substituent in the alkoxy group in which the hydrogen atom is optionally substituted by a substituent include an alkoxy group, an alkoxycarbonyl group, an amino group in which the hydrogen atom is substituted by a substituent, and a trialkoxysilyl group. 1 An embodiment in which the group is an unsubstituted alkoxy group is also one of the preferred embodiments of the present invention.

[0382] R 1 In the case of an amino group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is substituted by a substituent is more preferred.

[0383] Furthermore, it is preferred that at least one of the two hydrogen atoms in the amino group is substituted, and it is more preferred that only the other one is substituted.

[0384] Examples of the substituent in an amino group in which a hydrogen atom is optionally substituted by a substituent include a hydrocarbon group in which a hydrogen atom is optionally substituted, and more preferably an alkyl group in which a hydrogen atom is optionally substituted. The number of carbon atoms in the hydrocarbon group or alkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 3. Examples of the substituent in the hydrocarbon group or alkyl group include an alkoxy group, an alkoxycarbonyl group, an amino group in which a hydrogen atom is optionally substituted by a substituent, and a trialkoxysilyl group.

[0385] R 1 In the case of an alkylthio group in which a hydrogen atom is optionally substituted by a substituent, the number of carbon atoms in the alkylthio group is preferably 1 to 10, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 1 or 2.

[0386] Examples of the substituent in the alkylthio group in which the hydrogen atom is optionally substituted by a substituent include an alkoxy group, an alkoxycarbonyl group, an amino group in which the hydrogen atom is optionally substituted by a substituent, and a trialkoxysilyl group. 1 An embodiment in which the group is an unsubstituted alkylthio group is also one of the preferred embodiments of the present invention.

[0387] Among these, R 1are both hydrocarbon groups in which hydrogen atoms are optionally substituted by substituents, or R 1 One of them is a hydrocarbon group in which a hydrogen atom is optionally substituted by a substituent, and the other is an alkoxy group in which a hydrogen atom is optionally substituted by a substituent, an amino group in which a hydrogen atom is optionally substituted by a substituent, or an alkylthio group in which a hydrogen atom is optionally substituted by a substituent.

[0388] About R 1 Specific examples are described below, but the present invention is not limited to these.

[0389] [Chemical Formula 25]

[0390]

[0391] In formula (A-1), R 2 Each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0392] In formula (A-1), R 1 and R 2 At least two of them may be bonded to form a ring structure.

[0393] In the above embodiment, preferably R 1 bonded to each other to form a ring structure or R 1 One of them and R 2 One of them is bonded to form a ring structure.

[0394] R 1 When the cations are bonded to each other to form a ring structure, the formed ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 6-membered ring structure.

[0395] R 1 When the atoms are bonded to each other to form a ring structure, the formed ring structure preferably contains only carbon atoms or carbon atoms and oxygen atoms as ring-constituting atoms.

[0396] R 1 One of them and R 2 When one of them is bonded to form a ring structure, the formed ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure.

[0397] R 1 One of them and R 2 When one of them is bonded to form a ring structure, the formed ring structure preferably contains only carbon atoms as ring-constituting atoms.

[0398] [Synthesis Method]

[0399] Compound A can be synthesized, for example, by condensing an acid chloride or carboxylic acid of a dicarbonyl compound, or an acid chloride or carboxylic acid of a β-hydroxycarbonyl compound, with an alcohol compound or an amine compound using the method described in the Examples below. Alternatively, other known synthesis methods may be used, and the synthesis method is not particularly limited.

[0400] Furthermore, as compound A, a commercially available product can be used.

[0401] [Specific example]

[0402] Specific examples of the compound A are not particularly limited, and include compounds used in the examples described below.

[0403] 〔content〕

[0404] The content of compound A is preferably 0.01 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.02% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. In addition, the mode of 1% by mass or less is also one of the preferred modes of the present invention.

[0405] Furthermore, the content of compound A is preferably 0.02 to 40% by mass relative to the total mass of the specific resin. The lower limit is more preferably 0.03% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less. Furthermore, an embodiment of 1% by mass or less is also one of the preferred embodiments of the present invention.

[0406] When the resin composition includes a compound containing a Group IV element, the content of compound A is preferably 0.5 to 1000 mass % relative to the total mass of the compound containing the Group IV element. The lower limit is more preferably 1.0 mass % or more, further preferably 2.0 mass % or more, and particularly preferably 4.0 mass % or more. The upper limit is more preferably 500 mass % or less, further preferably 200 mass % or less, and particularly preferably 100 mass % or less. In addition, a mode of 30 mass % or less is also one of the preferred modes of the present invention.

[0407] Compound A may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[0408] <Compound B>

[0409] The first resin composition of the present invention preferably contains compound B.

[0410] The second resin composition of the present invention contains compound B.

[0411] Compound B is a compound represented by the following formula (B-1).

[0412] [Chemical Formula 26]

[0413]

[0414] In formula (B-1), R B1 Represents a tertiary alkyl group, R B2 Each independently represents a hydrogen atom or an organic group.

[0415] In formula (B-1), R B1 represents a tertiary alkyl group, preferably a group represented by the following formula (B1-1), more preferably a tert-butyl group.

[0416] [Chemical Formula 27]

[0417]

[0418] In formula (B1-1), R B3 Each independently represents an alkyl group, and * represents a bonding site to the benzene ring in formula (B-1).

[0419] In formula (B1-1), R B3 Each of the above groups is independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Furthermore, the above alkyl group is preferably a linear alkyl group.

[0420] In formula (B-1), R B2 In the case of an organic group, R B2 It is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and a ring structure. The hydrocarbon group is preferably an aliphatic saturated hydrocarbon group or a group represented by a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The ring structure may be either an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure, and more preferably an isocyanuric acid ring structure.

[0421] Furthermore, the compound represented by formula (B-1) is preferably a compound represented by the following formula (B-2) or a compound represented by the following formula (B-3).

[0422] [Chemical Formula 28]

[0423]

[0424] In formula (B-2), R B1 Represents a tertiary alkyl group, R B4 Each independently represents a hydrogen atom, an alkyl group or a hydroxyl group.

[0425] In formula (B-3), R B1 Each independently represents a tertiary alkyl group, R B4 Each independently represents a hydrogen atom, an alkyl group or a hydroxyl group, L represents an n-valent organic group, and n represents an integer of 2 or greater.

[0426] In formula (B-2), R B1 Preferred embodiments are the same as those in formula (B-1).

[0427] In formula (B-2), R B4 In the case of an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0428] In formula (B-3), R B1 Preferred embodiments are the same as those in formula (B-1).

[0429] In formula (B-3), R B4 In the case of an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0430] In formula (B-3), L is more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group formed by bonding at least one group in the following structures: N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom. In the following structure, * represents a bonding site to n benzene rings in formula (B-3).

[0431] [Chemical Formula 29]

[0432]

[0433] In formula (B-3), n is preferably 2-6, more preferably 2-4.

[0434] The molecular weight of compound B is preferably 100 to 2,000, more preferably 150 to 1,000, and even more preferably 200 to 800.

[0435] Specific examples of the compound represented by formula (B-1) are not particularly limited, and include 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N' -Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] phenyl) propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 4,4',4"-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl Butyl-4,4'-butylene-m-cresol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tert-butylhydroquinone, di-tert-butyl-p-cresol, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and the like.

[0436] The content of compound B of the present invention is preferably 0.1 to 5% by mass relative to the total solids content of the resin composition. The lower limit is more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. The upper limit is more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0437] The content of compound B is preferably 0.5 to 2000 mass % relative to the total mass of compound A. The lower limit is more preferably 1.0 mass % or more, further preferably 10.0 mass % or more, and particularly preferably 50.0 mass % or more. The upper limit is more preferably 500 mass % or less, further preferably 200 mass % or less, and particularly preferably 100 mass % or less. Furthermore, a mode of 30 mass % or less is also one of the preferred modes of the present invention.

[0438] Compound B may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[0439] <Compounds containing Group IV elements>

[0440] From the viewpoint of chemical resistance, the resin composition of the present invention may contain a compound containing a Group IV element.

[0441] Because compounds containing Group IV elements are unstable to heat and moisture, the coordination bond between the ligand and the titanium ion may break in the resin composition. In the present invention, it is believed that the combined use of Compound A allows the dicarbonyl compound, acting as a ligand, to rapidly coordinate even when the coordination bond in the complex breaks, thereby stabilizing the complex. Consequently, the stability of the compound containing a Group IV element in the composition is improved.

[0442] The compound containing an element of Group IV is preferably a compound containing titanium, zirconium or hafnium, more preferably a compound containing titanium.

[0443] Furthermore, the compound containing a Group IV element is preferably an organometallic complex, more preferably an organotitanium complex.

[0444] Specific examples of the compound containing titanium are shown in the following I) to VII).

[0445] I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred in view of the storage stability of the negative photosensitive resin composition and the good pattern that can be obtained. Specific examples include bis(triethanolamine)titanium diisopropoxide, di(n-butoxide)bis(2,4-pentanedione)titanium, titanium diisopropoxide bis(2,4-pentanedione), bis(tetramethylheptanedione)diisopropoxytitanium, bis(ethyl acetoacetate)diisopropoxytitanium, and the like.

[0446] II) Tetraalkoxytitanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetrakis[bis{2,2-(allyloxymethyl)butoxy}]titanium, and the like.

[0447] III) Titanocene compounds: for example, pentamethylcyclopentadienyltrimethoxytitanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0448] IV) Monoalkoxytitanium compounds: Examples include tris(dioctylphosphate)isopropoxytitanium and tris(dodecylbenzenesulfonate)isopropoxytitanium.

[0449] V) Titanium oxide compound: Examples include bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, and titanium phthalocyanine oxide.

[0450] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0451] VII) Titanate coupling agent: for example, isopropyl tridecylbenzenesulfonyl titanate.

[0452] Among the above-mentioned compounds I) to VII), from the viewpoint of exhibiting better chemical resistance, the compound containing titanium is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(η-butyloxy)titanium are preferred. 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0453] When the resin composition contains a compound containing a Group IV element, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or greater, heat resistance and chemical resistance are improved, while when the content is 10 parts by mass or less, storage stability is improved.

[0454] <Compound X>

[0455] From the viewpoint of improving developability, etc., the resin composition of the present invention preferably contains a compound represented by the following formula (X-3).

[0456] [Chemical formula 30]

[0457]

[0458] In formula (X-3), R X1 represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 10.

[0459] In formula (X-3), R X1 It is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group or an ethyl group.

[0460] Specific examples of compound X include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, and decyl 4-hydroxybutyrate.

[0461] The content of the compound X is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the specific resin.

[0462] <Polymerizable Compound>

[0463] The resin composition of the present invention preferably contains a polymerizable compound.

[0464] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0465] 〔Free radical crosslinking agent〕

[0466] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0467] 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 preferred. As the group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be mentioned.

[0468] Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0469] 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 also have three or more ethylenically unsaturated bonds.

[0470] 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.

[0471] 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.

[0472] 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.

[0473] As the specific 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.In addition, unsaturated carboxylic acid ester or amides with nucleophilic substituents such as hydroxyl, amino, sulfanyl and the addition reaction product of monofunctional or polyfunctional isocyanate or epoxy, and the dehydration condensation reaction product of monofunctional or polyfunctional carboxylic acid etc. can also be preferably used.In addition, unsaturated carboxylic acid ester or amides with electrophilic substituents such as isocyanate group or epoxy group and the addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols and the substitution reaction product of unsaturated carboxylic acid ester or amides with monofunctional or polyfunctional alcohols, amines, thiols and the disengagement substituents such as halo (halogeno group) or tosyloxy (tosyloxy group) and monofunctional or polyfunctional alcohols, amines, thiols can also be preferably used. Furthermore, as another example, a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. can also be used. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[0474] The radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher at normal pressure. Examples of the compound 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, and the contents are incorporated herein.

[0475] 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 thereof are incorporated herein.

[0476] 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. Oligomer types of these can also be used.

[0477] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains; SR-209, 231, and 239, bifunctional methacrylates having four ethyleneoxy 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.

[0478] Preferred free radical crosslinking agents include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Free radical crosslinking agents also include compounds having an amino structure or a thioether structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-B-01-105238.

[0479] The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyol and an unsaturated carboxylic acid, and more preferably a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyol. Among the free radical crosslinking agents having an acid group by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyol, it is particularly preferred that 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.

[0480] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. A radical crosslinking agent having 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.

[0481] 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.

[0482] In the present invention, the urea bond is *-NR N -C(=O)-NR N -*The bond represented by R N Each independently represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site to a carbon atom.

[0483] In the present invention, the carbamate bond is *-OC(=O)-NR N -*The bond represented by R Nrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom.

[0484] When the resin composition contains the crosslinking agent U, chemical resistance, resolution, etc. may be improved.

[0485] The mechanism for achieving the above effect is not clear, but it is considered that, for example, during curing by heating, a portion of the crosslinking agent U is thermally decomposed to generate amines, which promote cyclization of a polyimide precursor such as a polyimide precursor.

[0486] The crosslinking agent U may have only one urea bond or one urethane bond, one or more urea bonds and one or more urethane bonds, no urethane bond but two or more urea bonds, or no urea bond but two or more urethane bonds.

[0487] 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.

[0488] 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.

[0489] 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.

[0490] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. Preferably, it is (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, or maleimide, and more preferably, it is (meth)acryloyloxy.

[0491] 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.

[0492] 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.

[0493] The radical polymerizable group value (mass of the compound per 1 mol of the radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol.

[0494] 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.

[0495] 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.

[0496] The polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[0497] The crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.

[0498] [Chemical Formula 31]

[0499]

[0500] 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.

[0501] R U1 It is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0502] R N It is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0503] Z U1 Preferred are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of these, 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 of the groups.

[0504] 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.

[0505] Z U2 Preferred are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of these, 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 of the groups.

[0506] Examples of the hydrocarbon group include U1 The same hydrocarbon groups as those mentioned above are preferred in the same manner.

[0507] X is not particularly limited, but examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, and maleimide. Preferably, it is (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, or maleimide, and more preferably, it is (meth)acryloyloxy.

[0508] 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.

[0509] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0510] The crosslinking agent U also preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[0511] 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.

[0512] 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 ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethyleneoxy group.

[0513] 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.

[0514] Amide refers to -C(=O)-NR N - represents the bond. N In the case where the crosslinker U has an amide group, the crosslinker U can comprise, for example, RC(=O)-NR N -* represented by a group or *-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.

[0515] The crosslinking agent U may have two or more structures selected from hydroxyl groups, alkyleneoxy groups (polyalkyleneoxy groups when forming polyalkyleneoxy groups), amide groups, and cyano groups in the molecule, but it is also preferred that the molecule has only one structure.

[0516] 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 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").

[0517] 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 connected to at least one selected from a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group via a connecting group containing a urea bond or a carbamate bond (hereinafter also referred to as "connecting group L2-2").

[0518] When the crosslinking agent U includes 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 linking group L2-1 or the linking group L2-2 on the opposite side 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 preferably a hydrocarbon group, more preferably a hydrocarbon group having 18 or less carbon atoms, and further preferably a hydrocarbon group having 16 or less carbon atoms. 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.

[0519] In the case where the crosslinking agent U includes 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 having 20 or less carbon atoms is preferably a hydrocarbon group having 18 or less carbon atoms, and further preferably a hydrocarbon group having 16 or less carbon atoms. 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-mentioned 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.

[0520] Among these, the crosslinking agent U preferably has a hydroxyl group from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids.

[0521] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group.

[0522] 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.

[0523] 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.

[0524] 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.

[0525] The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole.

[0526] The hetero atom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

[0527] The above-mentioned aromatic group is preferably contained in, for example, a linking group that links two or more free radical polymerizing 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 free radical polymerizing group contained in the crosslinking agent U.

[0528] The number of atoms (linking 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.

[0529] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and two or more free radical polymerizable groups, the smallest number of atoms between the urea bond or urethane bond and the free radical polymerizable group (connection chain length) may be within the above range.

[0530] 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) chain of atoms connecting two atoms or groups of atoms to be connected. 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.

[0531] [Chemical Formula 32]

[0532]

[0533] 〔Axis of symmetry〕

[0534] The crosslinking agent U is also preferably a compound having a structure without an axis of symmetry.

[0535] "Crosslinker U lacks 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 the structural formula of crosslinker U is depicted on paper, "Crosslinker U lacks an axis of symmetry" means that the structural formula of crosslinker U cannot be depicted as having an axis of symmetry.

[0536] It is considered that since the cross-linking agent U does not have a symmetric axis, aggregation of the cross-linking agents U is suppressed in the composition film.

[0537] 〔Molecular weight〕

[0538] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0539] The method for producing the crosslinking agent U is not particularly limited, but the crosslinking agent U can be obtained, for example, 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.

[0540] Specific examples of the cross-linking agent U are shown below, but the cross-linking agent U is not limited thereto.

[0541] [Chemical Formula 33]

[0542]

[0543] [Chemical Formula 34]

[0544]

[0545] [Chemical Formula 35]

[0546]

[0547] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate in the resin composition.

[0548] 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, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and other bifunctional methacrylates having a urethane bond. Two or more of these may be used in combination as needed.

[0549] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of approximately 200.

[0550] 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, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or more at normal pressure is also preferred.

[0551] Examples of bifunctional or higher-functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0552] When a radical crosslinking agent is included, the content of the 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.

[0553] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used in combination, the total amount thereof is preferably within the above range.

[0554] 〔Other crosslinking agents〕

[0555] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0556] Other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, and are preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products through the photosensitization of the above-mentioned photoacid generator or photobase generator. It is preferably a compound having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products through the action of an acid or a base.

[0557] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0558] Examples of other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355, which are incorporated herein by reference.

[0559] 〔Polymerization initiator〕

[0560] The resin composition of the present invention preferably contains a polymerization initiator.

[0561] Furthermore, the resin composition of the present invention preferably contains a polymerization initiator and a sensitizer.

[0562] Generally speaking, owing to comprising heteroatoms in polymerization initiator or sensitizer, the polarity of these compounds is high, easily condenses in film.On the other hand, in the present invention, owing to compound A coexistence, it is possible to suppress the condensation of polymerization initiator and sensitizer.Although this reason is unclear, it is inferred that owing to interacting with polymerization initiator etc. by compound A, it is possible to reduce the mutual interactivity of polymerization inhibitor or sensitizer.As a result, it is thought that in the whole film, curing reaction is easily carried out evenly, oxygen permeability and hygroscopicity can be reduced, and the substrate adhesion after high temperature storage test is excellent.

[0563] The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.

[0564] 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 in the ultraviolet to visible regions is preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active free radicals may be used.

[0565] The photoradical polymerization initiator preferably contains at least one photopolymerization initiator 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 a known method. 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.

[0566] 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, hexaarylbimidazoles, 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, and the content is incorporated into this specification. 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.

[0567] 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.

[0568] 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.

[0569] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0570] As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0571] 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, and the contents thereof are incorporated into this specification.

[0572] As a photoradical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator, so they are particularly preferred.

[0573] 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. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Laid-Open No. 2000-066385, the compounds described in Japanese Translation of PCT International Publication No. 2004-534797, the compounds described in Japanese Patent Application Laid-Open No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Laid-Open No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515 are incorporated into this specification.

[0574] 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.

[0575] [Chemical Formula 36]

[0576]

[0577] Examples of commercially available 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 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds having the following structures can also be used.

[0578] [Chemical Formula 37]

[0579]

[0580] As the photoradical polymerization initiator, for example, oxime compounds having a fluorene ring, oxime compounds having a carbazole ring and a naphthalene ring skeleton in which at least one benzene ring is formed, and oxime compounds having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can be used.

[0581] 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.

[0582] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1Examples of the electron-withdrawing group include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups. Acyl and nitro groups are preferred. Acyl groups are more preferred due to the ease of forming a film with excellent light resistance, 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.

[0583] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2).

[0584] [Chemical Formula 38]

[0585]

[0586] 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 phosphinyl group, a carbamoyl group or a sulfamoyl group,

[0587] 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,

[0588] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0589] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0590] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 、R X11 、R X13 、R X14 A hydrogen atom.

[0591] 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.

[0592] Particularly preferred oxime compounds include oxime compounds having specific substituents disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group disclosed in JP-A-2009-191061, and the like, the contents of which are incorporated herein.

[0593] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from 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.

[0594] 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.

[0595] 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.

[0596] As the light radical polymerization initiator, a light radical polymerization initiator more than difunctional or trifunctional can be used. By using such a light radical polymerization initiator, since one molecule of the light radical polymerization initiator produces more than two free radicals, good sensitivity can be obtained. And, when using the compound of asymmetric structure, crystallinity declines and the solubility in the solvent etc. is improved, so it is difficult to separate out over time, thereby the time stability of the resin combination can be improved. Specific examples of bifunctional or trifunctional or higher-functional 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 compounds described in JP-A-2013-522445. The photoinitiator (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.

[0597] 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 alone or in combination. When containing two or more photopolymerization initiators, their total amount is preferably within the above range.

[0598] Furthermore, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further advanced by heating in an oven, a hot plate, or the like.

[0599] 〔Sensitizer〕

[0600] The resin composition may contain a sensitizer. The sensitizer absorbs specific active light rays and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes chemical changes and decomposes, generating free radicals, acids, or bases.

[0601] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole methine azo, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0602] 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-dimethylaminocinnamylindanone, p-dimethylaminoindanone, Benzyl indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene)benzothiazole, 2-(p-dimethylaminophenyl vinylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl Benzyl-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 Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0603] Also, other sensitizing pigments may be used.

[0604] 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.

[0605] 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.

[0606] Chain transfer agent

[0607] 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 used in RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer polymerization) polymerization, etc. can be used. These generate free radicals by supplying hydrogen to low-activity free radicals, or by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0608] 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.

[0609] 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 solids 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 content is preferably within the above range.

[0610] Furthermore, it is also one of the preferred aspects of the present invention that the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators.

[0611] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0612] By including a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure may be possible, radical polymerization may be facilitated during curing by a heating step described later, and performance such as chemical resistance may be improved.

[0613] When a photopolymerization initiator and a thermal polymerization initiator described below are contained, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0614] By including a photoradical polymerization initiator and a photoacid generator, performance such as resolution may be improved.

[0615] When the photopolymerization initiator and the photoacid generator are contained, the content of the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0616] [Thermal polymerization initiator]

[0617] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals using thermal energy, thereby initiating or promoting the polymerization reaction of polymerizable compounds. Adding a thermal free radical polymerization initiator also allows for polymerization of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0618] 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.

[0619] 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 resin composition may contain only one thermal polymerization initiator or two or more thermal polymerization initiators. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0620] <Base Generator>

[0621] 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.

[0622] In particular, when the resin composition contains a polyimide precursor, it is preferable to include a base generator. The inclusion of a thermal base generator in the resin composition can, for example, accelerate the cyclization reaction of the precursor by heating, thereby improving the mechanical properties and chemical resistance of the cured product. This improves the performance of the cured product as an interlayer insulating film for a redistribution layer in semiconductor packages, for example.

[0623] 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.

[0624] 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, benzylcarbamate compounds, nitrobenzylcarbamate 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 acyloxyimide compounds.

[0625] Specific examples of the nonionic base generator include the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355, which are incorporated herein by reference.

[0626] Examples of the base generator include the following compounds, but the base generator is not limited to these compounds.

[0627] [Chemical Formula 39]

[0628]

[0629] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0630] Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0631] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0632] [Chemical Formula 40]

[0633]

[0634] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0635] [Chemical Formula 41]

[0636]

[0637] Furthermore, from the viewpoint of storage stability and generation of a base by deprotection during curing, the base generator is preferably an amine in which the amino group is protected by a tert-butoxycarbonyl group.

[0638] 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]benzylamine, Examples of the present invention include, but are not limited to, alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 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-piperidinyl)-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 their derivatives in which the amino group is protected by a tert-butoxycarbonyl group.

[0639] When the resin composition contains a base generator, the content of the base 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.

[0640] The base generator may be used alone or in combination. When two or more base generators are used, the total amount is preferably within the above range.

[0641] <Solvent>

[0642] The resin composition of the present invention preferably contains a solvent.

[0643] The resin composition of the present invention preferably contains a solvent having at least one of an amide bond and a hydroxyl group. Such a solvent has excellent solubility for compound A and compound B and can suppress aggregation of these compounds.

[0644] Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0645] Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, 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, 3-ethoxypropionate), etc. Preferred examples include alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0646] 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.

[0647] Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0648] Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0649] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred example.

[0650] As amides, preferred examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0651] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0652] 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.

[0653] From the viewpoint of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[0654] In the present invention, preferably, it is one solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levulinone, and dihydrolevulinone, or a mixed solvent consisting of two or more thereof. Particularly preferred are the combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone, and dimethyl sulfoxide, or the combination 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 combined solvents.

[0655] Especially, from the viewpoint of the storage stability of resin combination etc., consider, the mode that comprises gamma-valerolactone as solvent is also one of preferred embodiment of the present invention.In this way, the content of gamma-valerolactone is preferably more than 50 mass % with respect to the gross mass of solvent, 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 is considered that the solubility of the composition such as contained specific resin in the resin combination etc. is determined.

[0656] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, 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, relative to the total mass of the solvent.

[0657] From the perspective of coating properties, the solvent content 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 desired thickness of the coating film and the coating method. When containing two or more solvents, it is preferred that the total amount of the solvents is within the above range.

[0658] <Metal Adhesion Improver>

[0659] 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 metal adhesion improvers 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.

[0660] 〔Silane coupling agent〕

[0661] 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, it is also preferred to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. 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 of a blocking agent derived from 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, etc. 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.).

[0662] [Chemical Formula 42]

[0663]

[0664] 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-acryloxypropyl The following examples include 1,2-dimethyl-1,3-butylene)propyltrimethoxysilane, 2,3-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, and 3-trimethoxysilylpropylpropylsuccinic anhydride. These may be used alone or in combination of two or more.

[0665] Furthermore, as the silane coupling agent, an oligomer-type compound having a plurality of alkoxysilyl groups can also be used.

[0666] Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0667] [Chemical Formula 43]

[0668]

[0669] 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.

[0670] R S1It is preferably a structure comprising a polymerizable group. As a polymerizable group, a group with an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group etc. 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, a (methyl) acrylamide group, a (methyl) acryloyloxy group etc. can be enumerated, preferably vinylphenyl, (methyl) acrylamide group or (methyl) acryloyloxy group, more preferably vinylphenyl or (methyl) acryloyloxy group, further preferably (methyl) acryloyloxy group.

[0671] R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

[0672] n represents an integer of 0 to 2, and is preferably 1.

[0673] Here, the structures of the plurality of repeating units represented by the formula (S-1) contained in the oligomer type compound may be the same.

[0674] 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.

[0675] As such an oligomer type compound, a commercially available product can be used, and examples of the commercially available product include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0676] Furthermore, as the silane coupling agent, a compound having a structure in which a hydrogen atom in an alkoxy group of an alkoxysilyl group is substituted with an organic group having at least one atom selected from oxygen, nitrogen, and sulfur atoms is also preferably used.

[0677] As such a compound, for example, the following compounds are exemplified.

[0678] [Chemical Formula 44]

[0679]

[0680] [Chemical Formula 45]

[0681]

[0682] [Chemical Formula 46]

[0683]

[0684] 〔Aluminum-based adhesive〕

[0685] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate aluminum diisopropoxide.

[0686] 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.

[0687] 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 it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above 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 using two or more, it is preferred that the total amount is within the above range.

[0688] <Migration Inhibitor>

[0689] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising 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 from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0690] The migration inhibitors mentioned here do not correspond to the compounds corresponding to compound A or compound B described above.

[0691] 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.

[0692] As the migration inhibitor, an ion capture agent that captures anions such as halogen ions can also be used.

[0693] 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 the contents of these compounds are incorporated into this specification.

[0694] Specific examples of the migration inhibitor include the following compounds.

[0695] [Chemical Formula 47]

[0696]

[0697] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass % relative to the total solid content of the resin composition.

[0698] 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.

[0699] <Polymerization Inhibitor>

[0700] 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.

[0701] The polymerization inhibitors mentioned here do not correspond to the compounds corresponding to compound A or compound B described above.

[0702] 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. These contents are incorporated herein.

[0703] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass % relative to the total solid content of the resin composition.

[0704] 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.

[0705] [Urea compounds, carbodiimide compounds, isourea compounds]

[0706] From the viewpoint of elongation at break and adhesion to metal or resin layers, the resin composition of the present invention may contain at least one compound selected from urea compounds, carbodiimide compounds, and isourea compounds (hereinafter also referred to as "urea compounds, etc.").

[0707] Among these, the resin composition of the present invention preferably further contains a urea compound.

[0708] The urea compounds and the like mentioned here do not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents.

[0709] In particular, the resin composition of the present invention preferably contains a urea compound. Since compound A captures metal ions from the metal substrate in the film, it can effectively suppress the migration of metal ions from the metal substrate to the cured product. On the other hand, since the urea compound has a moderate weak alkalinity, it can, for example, suppress corrosion of the metal substrate surface caused by trace acid components. In other words, it is speculated that by using a urea compound and a dicarbonyl compound together, it is possible to effectively achieve both the suppression of substrate metal ionization and the capture of ionized metal, resulting in excellent substrate adhesion after high-temperature storage testing.

[0710] Examples of urea compounds include compounds represented by the following formula (UR-1), examples of carbodiimide compounds include compounds represented by the following formula (UR-2), and examples of isourea compounds include compounds represented by the following formula (UR-3).

[0711] [Chemical Formula 48]

[0712]

[0713] In formula (UR-1), formula (UR-2) or formula (UR-3), R 11 and R 12 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, R 21 and R 22Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, R 31 and R 32 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

[0714] In formula (UR-1), R 11 and R 12 Each of the groups is independently preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having as a substituent at least one substituent selected from a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, and is more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0715] As R 11 and R 12 The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and further preferably an ethyl, isopropyl, tert-butyl or cyclohexyl group.

[0716] In formula (UR-1), R 11 and R 12 It may be an aliphatic hydrocarbon group having 2 to 7 carbon atoms, each independently having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group.

[0717] The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more substituents, but preferably has only one substituent.

[0718] In formula (UR-2), R 21 and R 22 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

[0719] In formula (UR-2), R 21 and R 22 It is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0720] In formula (UR-2), R 21 and R 22 The preferred embodiment of the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the above-mentioned aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above-mentioned substituent is respectively the same as R 11 and R12 Same as shown in the instructions.

[0721] In formula (UR-3), R 31 and R 32 It is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0722] In formula (UR-3), R 31 and R 32 The preferred embodiment of the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the above-mentioned aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above-mentioned substituent is respectively the same as R 11 and R 12 Same as shown in the instructions.

[0723] In formula (UR-3), R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and still more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0724] In formula (UR-3), R 33 , preferably methyl, ethyl, propyl, isopropyl, butyl or tert-butyl, more preferably ethyl.

[0725] Specific examples of the urea compound include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea, but are not limited thereto.

[0726] The total content of the urea compound and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, relative to 100 parts by mass of the specific resin.

[0727] The urea compound or the like may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, the total content of these bases is preferably within the above range.

[0728] <Light absorber>

[0729] The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength is reduced by exposure.

[0730] Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Laid-Open No. 2019-206689. These contents are incorporated into this specification.

[0731] 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 even more preferably 1 to 5 mass %.

[0732] <Other additives>

[0733] Resin combination of the present invention can comprise various additives as needed in the scope of obtaining 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, anti-agglomeration agent, 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 properties such as film physical properties. About these components, for example, can refer to the record of after 0183 paragraphs of Japanese Unexamined Patent Application Publication No. 2013 / 0034812 specification sheet of (0237 paragraphs of corresponding U.S. Patent Application Publication No. 2012-003225), the record of 0101~0104,0107~0109 paragraphs of Japanese Unexamined Patent Application Publication No. 2008-250074, these contents are incorporated in this specification. When coordinating these additives, its total content is preferably set to below the 3 mass % of the solids component of resin combination of the present invention.

[0734] Examples of these other additives include compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355, which are incorporated herein by reference.

[0735] <Characteristics of Resin Composition>

[0736] The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, more preferably 2,500mm 2 / s~8,000mm 2 / s. If it is within the above range, it is easy to obtain a highly uniform coating film. If it is 1,000mm 2 / s or more, for example, 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.

[0737] <Restrictions on Substances Contained in the Resin Composition>

[0738] 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.

[0739] Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0740] 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, but exclude metals contained in the form of complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0741] In addition, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material for forming the resin composition of the present invention, filtering the raw material for forming the resin composition of the present invention, lining the inside of an apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions that minimize contamination, etc.

[0742] Regarding the resin composition of the present invention, when considering its use as a semiconductor material, from the perspective of wiring corrosion resistance, 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. The amount present in the form of halogen ions is 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. Preferably, the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is within the above-mentioned range.

[0743] As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

[0744] Conventionally known containers can be used as containers for the resin composition of the present invention. To prevent the incorporation of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multilayer bottle having an inner wall composed of six layers of six different resins or a bottle having a seven-layer structure composed of six different resins. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[0745] <Cured Product of Resin Composition>

[0746] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0747] The cured product of the present invention is a cured product obtained by curing the resin composition.

[0748] Preferably, the curing of the resin composition is carried out by heating, more preferably the heating temperature is 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, rod, 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 formed by the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0749] 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.

[0750] Shrinkage [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0751] <Characteristics of Cured Resin Composition>

[0752] 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. When it is 70% or higher, the cured product may have excellent mechanical properties.

[0753] 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.

[0754] 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.

[0755] <Preparation of Resin Composition>

[0756] 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.

[0757] As a method for preparing the resin composition, for example, the method described in paragraphs 0283 to 0284 of International Publication No. 2022 / 210532 can be used. These descriptions are incorporated into this specification.

[0758] (Method for producing cured product)

[0759] The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition to a substrate to form a film.

[0760] The method for producing a cured product more preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a development step of developing the film exposed in the exposure step using a developer to form a pattern.

[0761] The method for producing a cured product 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.

[0762] Furthermore, the method for producing a cured product preferably includes the film forming step and the step of heating the film (heating step).

[0763] The heating step is preferably a step of heating the film at 50 to 450°C.

[0764] Furthermore, the method for producing a cured product of the present invention may further include a drying step, a post-exposure heating step, a post-development exposure step, a metal layer forming step, and the like, and steps described in International Publication No. 2022 / 210532.

[0765] Each step in the method for producing a cured product of the present invention can be performed, for example, by the same method as the steps described in paragraphs 0285 to 0325 of International Publication No. 2022 / 210532. These descriptions are incorporated into the present specification.

[0766] <Purpose>

[0767] Examples of fields in which the method for manufacturing the cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and insulating films for mounting purposes such as those described above, where patterns are formed by etching. For these applications, reference can be made, for example, to Science & Technology Co., Ltd.’s “Higher Functionality and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto, CMC Technical Library’s “Basics and Development of Polyimide Materials,” published November 2011, and Japan Polyimide and Aromatic Polymer Research Society’s “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0768] The method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of offset printing plates, screen printing plates, etc., for etching of molded parts, and for the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0769] (Laminate and method for producing laminate)

[0770] The laminate of the present invention refers to a structure having a plurality of layers formed from the cured product of the present invention.

[0771] The laminate is a laminate including two or more layers formed of a cured product, and may be a laminate including three or more layers.

[0772] Among the two or more layers formed of the above-mentioned cured product contained in the above-mentioned laminate, at least one layer is a layer formed of the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above-mentioned shrinkage, it is also preferred that all the layers formed of the cured product contained in the above-mentioned laminate are layers formed of the cured product of the present invention.

[0773] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.

[0774] The laminate of the present invention preferably comprises two or more layers formed of a cured product, and preferably comprises a metal layer between any of the layers formed of the cured product. The metal layer is preferably formed by the metal layer forming step.

[0775] That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer formed of the cured product before performing the method for producing a cured product multiple times. A preferred embodiment of the metal layer forming step is as described above.

[0776] Preferred examples of the laminate include a laminate having a layer structure in which at least three layers, namely, a layer formed of a first cured product, a metal layer, and a layer formed of a second cured product, are sequentially stacked.

[0777] The layer formed by the first cured product and the layer formed by the second cured product are preferably both layers formed by the cured product of the present invention. The resin composition of the present invention used to form the layer formed by the first cured product and the resin composition of the present invention used to form the layer formed by the second cured product may be compositions of the same composition or compositions of different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

[0778] <Lamination process>

[0779] The method for producing a laminated body of the present invention preferably includes a lamination step.

[0780] The lamination process is a series of processes including performing at least one of (a) a film forming process (layer forming process), (b) an exposure process, (c) a development process, (d) a heating process, and a post-development exposure process again in sequence on the surface of a pattern (resin layer) or a metal layer. Among these processes, at least one of (a) a film forming process, (d) a heating process, and a post-development exposure process may be repeated. Furthermore, (e) a metal layer forming process may be included after at least one of (d) a heating process and a post-development exposure process. The lamination process may further include the aforementioned drying process, etc., as appropriate.

[0781] When a lamination step is performed after the lamination step, a surface activation step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be discussed later.

[0782] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.

[0783] For example, the resin layer may be configured as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer. The resin layer may be configured as a structure of preferably 2 or more layers and 20 or less layers, more preferably 2 or more layers and 9 or less layers.

[0784] The composition, shape, film thickness, etc. of each of the above layers may be the same or different.

[0785] In the present invention, in particular, preferably after arranging metal layer, further form the cured product (resin layer) of the resin composition of the present invention to cover the mode of the above-mentioned metal layer.Specifically, can enumerate with (a) film forming process, (b) exposure process, (c) developing process, (d) heating process and development after exposure process at least one, (e) metal layer forming process order repeating mode or with (a) film forming process, (d) heating process and development after exposure process at least one, (e) metal layer forming process order repeating mode.By alternately stacking the lamination process and the metal layer forming process of the resin composition layer (resin layer) of the present invention, it is possible to alternately stack the resin composition layer (resin layer) of the present invention and the metal layer.

[0786] (Surface activation treatment process)

[0787] The method for producing a laminate of the present invention preferably includes a surface activation step of performing surface activation treatment on at least a portion of the metal layer and the resin composition layer.

[0788] The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and after the surface activation treatment step of the resin composition layer.

[0789] The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the exposed resin composition layer, or on at least a portion of each of the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a portion of the metal layer, and is preferably performed on a portion or all of the region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on the surface thereof can be improved.

[0790] The surface activation treatment is preferably also performed on a portion or all of the exposed resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve adhesion to a metal layer or resin layer provided on the surface after the surface activation treatment. In particular, when the resin composition layer is cured, such as when negative-tone development is performed, the surface treatment is less likely to damage the resin composition layer, and adhesion is easily improved.

[0791] The surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189, the contents of which are incorporated herein.

[0792] (Semiconductor device and manufacturing method thereof)

[0793] The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.

[0794] Furthermore, the present invention also discloses a method for producing a semiconductor device including the method for producing the cured product or the method for producing a laminate of the present invention.

[0795] As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[0796] Example

[0797] Hereinafter, the present invention will be further specifically described with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are weight references.

[0798] <Method for producing a polyimide precursor>

[0799] [Synthesis Example 1: Synthesis of polyimide precursor (resin 1)]

[0800] 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of diphthalic dianhydride (BPDA) were placed in a separable flask, along with 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran. The mixture was stirred at room temperature (25°C) and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

[0801] Next, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring under ice cooling. Subsequently, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) was suspended in 119.73 g of tetrahydrofuran and added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, followed by the addition of 136.83 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0802] The obtained reaction solution was added to 716.21 g of ethanol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. After filtering out the obtained precipitate, it was vacuum dried to obtain 80.3 g of powdered resin 1. The molecular weight of resin 1 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 20,000. 1 H-NMR confirmed that the structure of Resin 1 was represented by the following formula (P-1). Resins 1 with Mw of 5,000, 10,000, 30,000, 13,000, 14,000, 16,000, and 17,000 were synthesized by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether.

[0803] Furthermore, by adjusting the temperature and pH during synthesis, resin 1 having a Mw of 20,000 and cyclic imide structure amounts of 0.59, 0.32, 0.11, 0.06, 0.72, 1.26, 1.88, 2.10, and 2.39 mmol / g was synthesized.

[0804] [Synthesis Example 2A: Synthesis of Polyimide Precursor (Resin 2A)]

[0805] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diethylene glycol dimethyl ether (diglyme) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10±5°C over 60 minutes. The mixture was then stirred at room temperature for 2 hours. Subsequently, 10.0 g of ethanol was added, and the mixture was stirred at room temperature for 1 hour.

[0806] Next, 6000g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was filtered and dissolved in 500g of tetrahydrofuran. 6000g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was filtered again and dried at 45°C under reduced pressure for 3 days.

[0807] After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Thereafter, 3000 g of ethanol was added and the precipitate was filtered out. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto and stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was filtered out and dried at 45°C under reduced pressure for 24 hours to obtain 45.1 g of resin 2A.

[0808] pass 1 H-NMR confirmed that the structure of resin 2A was represented by the following formula (P-2). The molecular weight of resin 2A was measured by gel permeation chromatography (in terms of standard polystyrene) and the weight average molecular weight (Mw) was 20,000.

[0809] [Synthesis Example 2B: Synthesis of Polyimide Precursor (Resin 2B)]

[0810] Resin 2B having a structure represented by the following formula (P-2) was synthesized by the same method as in Synthesis Example 1 except that the compounds used were appropriately changed. 1 H-NMR confirmed that the structure of the resin 2B was represented by the following formula (P-2).

[0811] The Mw of resin 2B was 20,000.

[0812] [Synthesis Examples 3 to 9, 12 to 15: Synthesis of Polyimide Precursors (Resins 3 to 9, Resins 12 to 15)]

[0813] Except for appropriately changing the compounds used, resins 3 to 9 and resins 12 to 15 having structures represented by any one of the following formulas (P-3) to (P-9) and (P-12) to (P-15) were synthesized by the same method as in Synthesis Example 1.

[0814] The Mw of resin 3 is 20,000, the Mw of resin 4 is 20,000, the Mw of resin 5 is 20,000, the Mw of resin 6 is 20,000, the Mw of resin 7 is 20,000, the Mw of resin 8 is 20,000, the Mw of resin 9 is 20,000, the Mw of resin 12 is 20,000, the Mw of resin 13 is 20,000, the Mw of resin 14 is 20,000, and the Mw of resin 15 is 20,000. 1 H-NMR confirmed that the structures of Resins 3 to 9 and Resins 12 to 15 were represented by the following formulas (P-3) to (P-9) and (P-12) to (P-15), respectively.

[0815] [Synthesis Example 10: Synthesis of polyimide (resin 10)]

[0816] In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Subsequently, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours and then at 45°C for another 3 hours. Subsequently, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. The mixture was then diluted by adding 50 g of N-methylpyrrolidone (NMP).

[0817] The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was filtered and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C under reduced pressure for 1 day to obtain resin 10. The molecular weight of resin 10 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. 1 H-NMR confirmed that the structure of the resin 10 was represented by the following formula (P-10).

[0818] [Synthesis Example 11: Synthesis of polyimide (resin 11)]

[0819] Resin 11 having a structure represented by the following formula (P-11) was synthesized by the same method as in Synthesis Example 10 except that the compounds used were appropriately changed. 1H-NMR confirmed that the structure of the resin 11 was represented by the following formula (P-11).

[0820] The Mw of resin 11 was 20,000.

[0821] [Chemical Formula 49]

[0822]

[0823] [Chemical Formula 50]

[0824]

[0825] [Chemical Formula 51]

[0826]

[0827] <Examples and Comparative Examples>

[0828] In each example, the components described in the following table were mixed to obtain each resin composition. In addition, in the comparative example, the components described in the following table were mixed to obtain a comparative composition.

[0829] Specifically, the content (compound amount) of each component described in the table except the solvent is set to the amount (parts by mass) described in the column "parts by mass" in each column of the table.

[0830] The content (amount added) of the solvent is set to the value (mass %) at which the solid content concentration of the composition becomes the "Solid Content Concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent is set to the ratio described in the "Ratio" column in the table.

[0831] The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter having a pore width of 0.8 μm.

[0832] In the table, “-” indicates that the composition does not contain the corresponding component.

[0833] The total amount of the cyclic imide structure and cyclic isoimide in the polyimide precursor is described in the column "Amount of cyclic imide in resin". The unit is mmol / g.

[0834]

[0835]

[0836]

[0837]

[0838]

[0839]

[0840]

[0841]

[0842]

[0843]

[0844]

[0845] The details of each component described in the table are as follows.

[0846] 〔Resin〕

[0847] Resins 1 to 15: Resins 1 to 15 obtained by the above-mentioned synthesis examples

[0848] [Monomer (polymerizable compound)]

[0849] M-1 to M-4: Compounds with the following structures

[0850] [Chemical Formula 52]

[0851]

[0852] DPHA: Dipentaerythritol hexaacrylate

[0853] [Polymerization initiator or photoacid generator]

[0854] I-1 to I-9: Compounds with the following structures

[0855] [Chemical Formula 53]

[0856]

[0857] [Thermal alkali generator]

[0858] A-1 to A-5: Compounds with the following structures

[0859] [Chemical Formula 54]

[0860]

[0861] 〔Polymerization inhibitor〕

[0862] ·E-9: Compound with the following structure

[0863] [Chemical Formula 55]

[0864]

[0865] B-1 to B-5: compounds of the following structures. B-4 and B-5 are compounds corresponding to compound B.

[0866] [Chemical Formula 56]

[0867]

[0868] 〔Silane coupling agent (metal adhesion improver)〕

[0869] C-1 to C-7: Compounds of the following structures. (Me represents a methyl group, and Et represents an ethyl group)

[0870] [Chemical Formula 57]

[0871]

[0872] 〔Migration inhibitor〕

[0873] D-1 to D-3: Compounds with the following structures

[0874] [Chemical Formula 58]

[0875]

[0876] 〔additive〕

[0877] ·E-1 to E-6, E-10 to E-17: Compounds with the following structures

[0878] [Chemical Formula 59]

[0879]

[0880] E-7: 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'-hexanol ester with 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid

[0881] E-8: Synthetic product of the following

[0882] <Additive: Synthesis of Diazonaphthoquinone Compound E-8>

[0883] To the flask was added 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylene)bisphenol (Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.). Next, 46.93 g (174.9 mmol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring. The mixture was added dropwise to the flask over 30 minutes using a dropping funnel and stirred at an internal temperature of 30°C for 30 minutes. Hydrochloric acid was then added dropwise, and the mixture was stirred for a further 30 minutes. Next, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker. The filtrate obtained by filtering the hydrochloride from the reaction solution was added dropwise. The precipitate was filtered, washed with water, and vacuum-dried at 40°C for 50 hours to obtain diazonaphthoquinone compound E-8.

[0884] [Compound A]

[0885] F-1 to F-23: Compounds of the following structures. F-1 to F-23 are compounds corresponding to compound A (wherein, in the structural formula, Et represents an ethyl group).

[0886] FR-1: A compound having the following structure. FR-1 is a compound that does not correspond to Compound A.

[0887] [Chemical Formula 60]

[0888]

[0889] Solvent

[0890] NMP: N-methyl-2-pyrrolidone

[0891] EL: Ethyl lactate

[0892] DMSO: dimethyl sulfoxide

[0893] GBL: gamma-butyrolactone

[0894] GVL: γ-valerolactone

[0895] MDMPA: 3-methoxy-N,N-dimethylpropionamide

[0896] toluene: toluene

[0897] <Evaluation>

[0898] [Evaluation of Adhesion after Heat Resistance Test]

[0899] The resin composition or comparative composition prepared in each embodiment and comparative example was applied to a copper substrate in a layered form by spin coating to form a resin composition layer or a comparative composition layer. The copper substrate on which the resin composition layer or comparative composition layer was formed was dried at 100°C for 5 minutes on a hot plate to form a resin composition layer or a comparative composition layer having a uniform thickness as described in the "Thickness (μm)" column of the table on the copper substrate. 2 The resin composition layer or the comparative composition layer on the copper substrate was exposed to light having an exposure wavelength (nm) described in the "Exposure Wavelength (nm)" column of the table, and a non-mask portion having a square size of 100 μm was formed using an exposure energy of 100 μm in the example described as "CP" in the "Developer" column of the table, and a mask portion having a square size of 100 μm was formed using a photomask in the example described as "T" in the "Developer" column of the table.

[0900] In the example where "M" is written in the exposure condition column, exposure was performed using a stepper as a light source.

[0901] In the example described as "D" in the exposure condition column, laser direct imaging exposure was performed in an area of ​​100 μm square using a direct exposure device (ADTEC DE-6UH III) as a light source without using a photomask.

[0902] The film was then developed for 60 seconds using the developer described in the table to obtain a 100 μm square resin layer. “CP” in the table refers to cyclopentanone, and “T” in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0903] In the examples where a numerical value is recorded in the "Curing Temperature" column, the exposed resin composition layer is heated at a heating rate of 10°C / minute in a nitrogen environment using a hot plate. After reaching the temperature recorded in the "Curing Temperature (°C)" column of the table, the temperature is maintained for the time described in the "Curing Time (min)" of the table to obtain a cured product.

[0904] In the examples where "IR" is recorded in the "Curing temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCERIKO, Inc., RTP-6) was used to heat the resin film obtained in each example at a heating rate of 10°C / minute in a nitrogen environment. After reaching 230°C, the above temperature was maintained for the time shown in the "Curing time (min)" in the table to obtain a cured product.

[0905] The obtained copper substrate with the cured product was placed in a tank at a temperature of 175°C under atmospheric conditions for 192 hours. Shear force was measured on a 100 μm square cured product on the copper substrate using a bonding strength tester (manufactured by XYZTEC, CondorSigma) at 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion after heat resistance test" column of the table. It can be said that the greater the shear force, the better the adhesion of the cured film after the heat resistance test.

[0906] -Evaluation Criteria-

[0907] A: Shear force exceeds 30 gf.

[0908] B: Shearing force exceeds 25 gf and is 30 gf or less.

[0909] C: Shearing force exceeds 20 gf and is 25 gf or less.

[0910] D: Shearing force is 20 gf or less.

[0911] Also, 1gf is 0.00980665N.

[0912] [Evaluation of the amount of voids at the copper substrate / cured material interface after the heat resistance test]

[0913] The resin composition or comparative composition prepared in each embodiment and comparative example was applied in a layered form on an 8-inch silicon wafer with a Cu wiring pattern (L / S (line and space) 10 μm (thickness 5 μm) (comb-shaped) silicon wafer with a Cu wiring pattern) that had not been pre-treated by spin coating, thereby forming a resin composition layer or a comparative composition layer. The Si wafer having the resin composition layer or the comparative composition layer was dried at 100°C for 5 minutes on a heating plate to form a resin composition layer or a comparative composition layer having a uniform thickness as described in the "Film Thickness (μm)" column of the table on the substrate (Si wafer). At 500mJ / cm 2 The exposure energy was set to "CP" in the "Developer" column of the table, and a photomask having a non-mask portion having a square area of ​​100 μm was used. In the example described as "T" in the "Developer" column of the table, a photomask having a mask portion having a square area of ​​100 μm was used. The resin composition layer or the comparison composition layer on the Si wafer was exposed to light having an exposure wavelength (nm) described in the "Exposure Wavelength (nm)" column of the table.

[0914] In the example where "M" is written in the exposure condition column, exposure was performed using a stepper as a light source.

[0915] In the example described as "D" in the exposure condition column, laser direct imaging exposure was performed in an area of ​​100 μm square using a direct exposure device (ADTEC DE-6UH III) as a light source without using a photomask.

[0916] The film was then developed for 60 seconds using the developer described in the table to obtain a 100 μm square resin layer. “CP” in the table refers to cyclopentanone, and “T” in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0917] In the examples where a numerical value is recorded in the "Curing Temperature" column, the exposed resin composition layer is heated at a heating rate of 10°C / minute in a nitrogen environment using a hot plate. After reaching the temperature recorded in the "Curing Temperature (°C)" column of the table, the temperature is maintained for the time described in the "Curing Time (min)" of the table to obtain a cured product.

[0918] In the examples where "IR" is recorded in the "Curing temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCERIKO, Inc., RTP-6) was used to heat the resin film obtained in each example at a heating rate of 10°C / minute in a nitrogen environment. After reaching 230°C, the above temperature was maintained for the time shown in the "Curing time (min)" in the table to obtain a cured product.

[0919] The obtained Si wafer with the cured product was placed in a bath at a temperature of 175° C. under atmospheric pressure for 192 hours.

[0920] Cross-sectional SEM (scanning electron microscope) measurement was performed to evaluate the void area ratio between the Cu wiring pattern and the cured product. The void area ratio was calculated using the following formula.

[0921] Void area ratio (%) = (area of ​​voids observed by SEM measurement) / (total area of ​​cured product) × 100

[0922] The void area ratio values ​​obtained were evaluated according to the following evaluation criteria. The evaluation results are reported in the "Void Amount after Heat Resistance Test" column in the table. It can be said that the smaller the void area ratio, the better the adhesion of the cured film after the heat resistance test, and it can be said that voids are less likely to form between the metal layer and the cured product even after a long period of time.

[0923] -Evaluation Criteria-

[0924] A: The void area ratio is 0.5% or less.

[0925] B: The void area ratio is more than 0.5% and 1% or less.

[0926] C: The void area ratio is more than 1% and 2% or less.

[0927] D: The void area ratio exceeds 2%.

[0928] From the above results, it is understood that the cured product formed from the resin composition of the present invention has excellent adhesion over a long period of time.

[0929] The comparative composition according to Comparative Example 1 does not contain a compound corresponding to Compound A. It is understood that such a comparative composition has poor adhesion after a long period of time.

[0930] <Example 201>

[0931] The resin composition used in Example 1 was applied to the copper thin layer surface of a resin substrate having a copper thin layer formed thereon by spin coating. After drying at 100°C for 5 minutes to form a 20 μm thick photosensitive film, it was exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a line width of 10 μm). After exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.

[0932] Next, the temperature was raised at a rate of 10° C. / min in a nitrogen atmosphere to 230° C., and then maintained at 230° C. for 180 minutes to form a redistribution layer interlayer insulating film having excellent insulation properties.

[0933] Furthermore, a semiconductor device was manufactured using the interlayer insulating film for redistribution, and it was confirmed that the device was functioning normally.

[0934]

[0935] [Synthesis Example B-1: Synthesis of Comparative Polyimides (B-1) to (B-2)]

[0936] Comparative polyimides (B-1) and (B-2) were synthesized by the same method as that for polyimide (P-1) except that the raw materials used were appropriately changed.

[0937] The comparative polyimides (B-1) and (B-2) are resins having repeating units represented by the following formulas (B-1) and (B-2). 1 The structure of each repeating unit was confirmed by H-NMR spectroscopy. In the following structures, the subscripts in brackets represent the molar ratio of each structure.

[0938] The weight average molecular weight (Mw) of the comparative polyimide (B-1) was 7,500, and the Mw of the comparative polyimide (B-2) was 50,000.

[0939] [Chemical Formula 72]

[0940]

[0941] [Table 1]

[0942] resin Ethylenically unsaturated bond value (mmol / g) Molar amount of oxygen atoms / weight average molecular weight (mmol / g) P-1 1.23 8.6 P-2 1.41 9.2 P-3 1.32 7.9 P-4 1.94 - P-5 0.71 8.6 P-6 0.83 9.1 P-7 1.21 10.9 P-8 1.20 8.4 P-9 1.43 8.6 P-10 1.51 9.0 P-11 1.39 8.4 P-12 1.15 8.6 P-13 1.11 8.3 P-14 1.03 9.5 P-15 1.17 8.8 P-16 1.17 8.8 P-17 1.12 7.9 B-1 1.23 11.1 B-2 0.00 12.0

[0943] <Examples and Comparative Examples>

[0944] In each example, the components described in the following table were mixed to obtain each resin composition. In addition, in each comparative example, the components described in the following table were mixed to obtain each comparative composition.

[0945] Specifically, the content of each component described in the table is set to the amount (parts by mass) described in the "parts by mass" column of each column in the table.

[0946] The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter having a pore width of 0.5 μm.

[0947] In the table, “-” indicates that the composition does not contain the corresponding component.

[0948] [Table 2]

[0949]

[0950] [Table 3]

[0951]

[0952] [Table 4]

[0953]

[0954] [Table 5]

[0955]

[0956] [Table 6]

[0957]

[0958] [Table 7]

[0959]

[0960] [Table 8]

[0961]

[0962] [Table 9]

[0963]

[0964] [Table 10]

[0965]

[0966] [Table 11]

[0967]

[0968] [Table 12]

[0969]

[0970] [Table 13]

[0971]

[0972] The details of each component described in the table are as follows.

[0973] 〔Resin〕

[0974] ·P1~P17、B-1~B-2: In the above synthesized P-1~P-17、B-1~B-2

[0975] 〔Polymerization initiator〕

[0976] C-1 to C-8: Compounds with the following structures

[0977] [Chemical Formula 73]

[0978]

[0979] 〔Polymerizable compounds〕

[0980] D-1: SR-209 (manufactured by Sartomer Company, Inc.)

[0981] D-2: LIGHT ACRYLATE 4EG-A (manufactured by KYOEISHA CHEMICAL CO., LTD.)

[0982] D-3: NOD-N (manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0983] ·D-4: A-DOD-N (manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0984] D-5: DDD (1,12-dodecanediol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[0985] D-6: A-DCP (manufactured by Shin Nakamura Chemical Co., Ltd.)

[0986] ·D-7: A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)

[0987] D-8: A-GLY-9E (manufactured by Shin Nakamura Chemical Co., Ltd.)

[0988] D-9: A-TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.)

[0989] D-10: NK Ester A-BPE-30 (manufactured by Shin Nakamura Chemical Co., Ltd.)

[0990] D-11: BR-31 (manufactured by DKS Co. Ltd.)

[0991] [Thermal alkali generator]

[0992] ·E-1: Compound with the following structure

[0993] [Chemical Formula 74]

[0994]

[0995] [Silane coupling agent]

[0996] ·F-1: Compound with the following structure

[0997] F-2: X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0998] F-3: KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0999] F-4: KBM-1083 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1000] F-5: KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1001] F-6: KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1002] [Chemical Formula 75]

[1003]

[1004] 〔Polymerization inhibitor〕

[1005] G-1 to G-4: Compounds with the following structures

[1006] [Chemical Formula 76]

[1007]

[1008] 〔Migration inhibitor〕

[1009] H-1 to H-4: Compounds with the following structures

[1010] [Chemical Formula 77]

[1011]

[1012] 〔Other additives〕

[1013] I-1: Compound having the following structure (titanium compound)

[1014] I-2: Compound having the following structure (titanium compound)

[1015] I-3: TC-750 (manufactured by Matsumoto Fine Chemical Co. Ltd.)

[1016] I-4: 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobis(1H-indene)-5,5',6,6',7,7'-hexanol ester with 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid (NQD (naphthoquinone diazide))

[1017] I-5: Compound with the following structure

[1018] I-6: PERCUMYL D (manufactured by NOF CORPORATION)

[1019] I-7: F-554 (fluorine-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)

[1020] I-8: KF-6000 (silicone-based surfactant, manufactured by Shin-Ftsu Chemical Co., Ltd.)

[1021] I-9: Triphenyl phosphate

[1022] [Chemical Formula 78]

[1023]

[1024] Solvent

[1025] GBL: gamma-butyrolactone

[1026] GVL: γ-valerolactone

[1027] DMSO: dimethyl sulfoxide

[1028] NMP: N-methyl-2-pyrrolidone

[1029] [Curing method]

[1030] N2 oven: CLH-21 (manufactured by Koyo)

[1031] Vacuum oven: PB12 (manufactured by Yield Engineering Systems)

[1032] IR oven: RTP-6 (manufactured by ADVANCE RIKO, Inc.)

[1033] <Evaluation>

[1034] 〔Determination of dissolution rate〕

[1035] In each embodiment and comparative example, a composition having the composition described in the table was coated on a silicon wafer by the method described in the "Coating method" column of the table, and heated to the temperature and time described in the "Temperature" of "SB" and the "Time" column of "SB" in the table, thereby forming a resin composition layer (film) with a thickness of 10 μm on the silicon wafer.

[1036] The silicon wafer formed with the obtained resin composition layer was immersed in cyclopentanone for 15 seconds. After the immersion, the wafer was rotated at 2000 rpm for 10 seconds. The film thickness of the resin composition layer after immersion was measured at 10 points on the coating surface using an ellipsometer (KT-22 manufactured by Foothill Company). The arithmetic mean value was obtained. The dissolution rate (μm / sec) was calculated based on the film thickness based on the above-mentioned measurement and the film thickness before immersion, i.e., 10 μm. The measurement results are recorded in the "composition dissolution rate" column of the table.

[1037] Furthermore, GBL (γ-butyrolactone) solutions of the resins used in the Examples and Comparative Examples were used to form resin layers (films) by the same method as above, and the dissolution rates were measured. The measurement results are reported in the "Dissolution Rate" column under "Resin" in the table.

[1038] [Evaluation of resolution]

[1039] In each embodiment and comparative example, the resin composition of the composition described in the table was applied to a silicon wafer by the method described in the "coating method" column of the table, and heated to the temperature and time described in the "temperature" of "SB" and the "time" column of "SB" of the table, so that the film thickness of the cured product obtained on the silicon wafer became 3 μm. The coating conditions were appropriately adjusted. A square through-hole mask having a pattern of 0.5 μm intervals of 0.5 to 10 μm was used, and an i-ray stepper (manufactured by Canon Inc.: FPA-3000i5) was used at a temperature of 100 to 800 mJ / cm 2 In the range of 50mJ / cm 2 The obtained resin composition layer was exposed to light at each exposure dose on the scale.

[1040] Thereafter, the film was developed with cyclopentanone for 30 seconds and rinsed with PGMEA (propylene glycol monomethyl ether acetate) for 30 seconds by the method described in the "Method" column of "Development" in the table.

[1041] Furthermore, using the apparatus described in the "Method" column of "Curing" in the table, heating was performed at the temperature and time described in the "Temperature" and "Time" columns of "Curing" in the table to obtain a cured product with a film thickness of 3 μm.

[1042] The minimum mask opening diameter of the resulting cured product was determined by observing the cross-section of the opening pattern using a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The minimum mask opening diameter was defined as the smallest mask diameter among those that formed the opening pattern at at least one exposure level among the aforementioned exposure levels. The evaluation results are reported in the "Resolution" column in the table.

[1043] (Evaluation Criteria)

[1044] A: The minimum mask opening diameter is 3 μm or less.

[1045] B: The minimum mask opening diameter is more than 3 μm and 5 μm or less.

[1046] C: The minimum mask opening diameter exceeds 5 μm.

[1047] [Evaluation of pattern collapse resistance]

[1048] In each of the Examples and Comparative Examples, in the "Resolution Evaluation" described above, a resin pattern with a film thickness of 3 μm was obtained by the same method except that the square via mask was changed to a line and space mask with a 0.5 μm interval of 0.5 to 10 μm.

[1049] The maximum mask collapse width of the obtained resin pattern was determined by observing the cross-section of the line and space regions using a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). Evaluation was performed according to the following evaluation criteria. The maximum mask collapse width was defined as the largest mask diameter at which pattern collapse was observed at at least one exposure among the above exposures. The evaluation results are reported in the "Pattern Collapse Resistance" column in the table.

[1050] (Evaluation Criteria)

[1051] A: The maximum mask collapse diameter is 2 μm or less.

[1052] B: The maximum mask collapse diameter is more than 2 μm and 3 μm or less.

[1053] C: The maximum mask collapse diameter exceeded 3 μm.

[1054] [Evaluation of pattern shape]

[1055] In each of the Examples and Comparative Examples, a resin pattern having a film thickness of 3 μm was obtained by the same method as in the above-mentioned “Evaluation of Resolution”.

[1056] The taper angle of the opening of the 5μm square through-hole in the obtained resin pattern was measured. Among the results of exposure at each of the above exposure doses, the taper angle at at least one exposure dose with a taper angle of 80° or greater and less than 90° was designated "A," and the remaining tapers were designated "B." The taper angle was calculated by cutting the substrate having the above resin pattern formed thereon and observing the cross-section with a scanning electron microscope. The evaluation results are reported in the "Pattern Shape" column in the table.

[1057] From the above results, it is understood that the resin composition of the present invention provides a cured product having excellent pattern resolution.

[1058] Regarding the resin composition in Comparative Example 1, the dissolution rate of a 10 μm thick film obtained from the composition in cyclopentanone exceeded 0.55 μm / sec, and the dissolution rate of the included resin in a 10 μm thick film in cyclopentanone exceeded 0.2 μm / sec. This indicates that the resolution of this comparative example is poor.

[1059] Regarding the resin composition in Comparative Example 2, the dissolution rate of a 10 μm thick film obtained from the composition in cyclopentanone was less than 0.01 μm / sec, and the dissolution rate of the contained resin in a 10 μm thick film in cyclopentanone was less than 0.01 μm / sec. This indicates that the resolution of this comparative example is poor.

[1060] <Example 101>

[1061] The resin composition used in Example 1 was applied in a layered form to the surface of a substrate having a copper wiring with a 2 μm line and space pattern formed thereon by spin coating, and dried at 110° C. for 5 minutes to form a 5 μm thick resin composition layer. The resin composition was then irradiated using an i-ray stepper (Canon Inc.: FPA-3000i5) at a wavelength of 365 nm and a temperature of 300 mJ / cm 2 The film was exposed under 40°C (140°F) of 1% CO 2 and then developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The film was then heated at a rate of 10°C / minute in a nitrogen atmosphere until it reached 230°C, where it was maintained at 230°C for 3 hours to form a redistribution interlayer insulating film. This redistribution interlayer insulating film exhibited excellent insulating properties.

[1062] Furthermore, semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, and normal operation was confirmed.

Claims

1. A resin composition comprising: At least one resin selected from polyimide and its precursor; polymeric compounds; and polymerization initiator, The dissolution rate of a 10 μm-thick film obtained from the resin composition in cyclopentanone is 0.01 μm / sec to 0.55 μm / sec.

2. A resin composition comprising: At least one resin selected from polyimide and its precursor; polymeric compounds; and polymerization initiator, The resin composition includes, as the resin, a resin having a film thickness of 10 μm and a dissolution rate in cyclopentanone of 0.01 μm / sec to 0.2 μm / sec.

3. The resin composition according to claim 1 or 2, wherein The weight average molecular weight of the resin is greater than or equal to 8,000 and less than 30,000.

4. The resin composition according to claim 1 or 2, wherein The resin is a resin having a ring structure having 5 or more ring atoms in a side chain.

5. The resin composition according to claim 1 or 2, wherein The resin is a resin containing a structure represented by the following formula (A-1), In formula (A-1), L A1 represents a single bond or an m+1 valent linking group, Cy each independently represents a ring structure having 5 or more ring atoms, the ring structure being a ring structure optionally having a substituent, m represents an integer of 1 or more, and * represents a bonding site with another structure.

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 repeating unit represented by the following formula (1-1), In formula (1-1), X 1 is a tetravalent organic group, Y 1 It is an organic group containing a group having an ethylenically unsaturated bond.

8. The resin composition according to claim 7, wherein The value of the molar amount of oxygen atoms in the resin / weight average molecular weight is 9.7 mmol / g or less.

9. The resin composition according to claim 7, wherein Y in the formula (1-1) 1 It includes a ring structure having 5 or more ring atoms.

10. The resin composition according to claim 7, wherein Y in the formula (1-1) 1 Contains vinylphenyl.

11. The resin composition according to claim 7, wherein Y in the formula (1-1) 1 Containing the structure represented by formula (B-1) or (B-2), In formula (B-1), R 1 Each independently represents an organic group containing a group having an ethylenically unsaturated bond, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, n1+n2 is an integer of 1 to 6, and * represents a bonding site with other structures. In formula (B-2), R 1 Each independently represents an organic group containing a group having an ethylenically unsaturated bond, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, n1+n2 is an integer of 1 to 6, R 2 Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site to another structure.

12. The resin composition according to claim 11, further comprising a repeating unit represented by the following formula (1-2): In formula (1-2), X 2 is a tetravalent organic group, Y 2 is a divalent organic group having no ethylenically unsaturated bond, X 2 and Y 2 At least one of them contains a group obtained by removing two or more hydrogen atoms from the structure represented by the following formula (C-1), In formula (C-1), Z 1 ~Z 3 Each is independently a single bond or a divalent linking group, and each of the four benzene rings described in formula (C-1) may have a substituent.

13. A resin composition comprising: A resin having a repeating unit represented by the following formula (1-3) and a structure represented by the following formula (A-1); polymeric compounds; and polymerization initiator, In formula (A-1), L A1 represents a single bond or an m+1 valent linking group, Cy each independently represents a ring structure having 5 or more ring atoms, the ring structure being a ring structure optionally having a substituent, m represents an integer of 1 or more, and * represents a bonding site with another structure. In formula (1-3), X 3 is a tetravalent organic group, Y 3 is a divalent organic group containing a vinylphenyl group, Y 3 Containing the structure represented by formula (B-1) or (B-2), In formula (B-1), R 1 Each independently represents an organic group containing a group having an ethylenically unsaturated bond, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, n1+n2 is an integer of 1 to 6, and * represents a bonding site with other structures. In formula (B-2), R 1 Each independently represents an organic group containing a group having an ethylenically unsaturated bond, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, n1+n2 is an integer of 1 to 6, R 2 Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site to another structure.

14. The resin composition according to claim 1, 2 or 13, wherein The resin composition contains a radical polymerizable compound as the polymerizable compound, and the content of the radical polymerizable compound is 8 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the resin.

15. The resin composition according to claim 1, 2 or 13, wherein The resin composition includes a photoradical polymerization initiator as the polymerization initiator and a radical polymerizable compound as the polymerizable compound.

16. The resin composition according to claim 15, wherein The radical polymerizable compound includes two or more (meth)acryloyl groups.

17. The resin composition according to claim 15, wherein The resin composition includes an oxime compound as the photoradical polymerization initiator.

18. The resin composition according to claim 15, wherein The resin composition includes a compound having a ketoxime group as the photoradical polymerization initiator.

19. The resin composition according to claim 1, 2 or 13, wherein The resin composition includes a resin having an ethylenically unsaturated bond value of 0.5 mmol / g to 2.0 mmol / g or less as the resin.

20. The resin composition according to claim 1, 2 or 13, which is used for forming an interlayer insulating film for a redistribution layer.

21. A cured product obtained by curing the resin composition according to claim 1, 2 or 13. 22 . A laminate comprising two or more layers formed of the cured product according to claim 21 , wherein a metal layer is provided between any of the layers formed of the cured product.

23. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to claim 1, 2 or 13 on a substrate to form a film.

24. The method for producing a cured product according to claim 23, comprising: An exposure step of selectively exposing the film to light; and In the development step, the film is developed using a developer to form a pattern. 25 . The method for producing a cured product according to claim 23 , comprising a heating step of heating the film at 50° C. to 450° C.

26. A method for producing a laminate, comprising the method for producing a cured product according to claim 23.

27. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 23.

28. A semiconductor device comprising the cured product according to claim 21.

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