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

Abstract

Provided are a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device, the resin composition containing at least one resin selected from the group consisting of polyimides and precursors thereof, a polymerizable compound, and a photopolymerization initiator, the polymerizable compound has an equivalent weight of an ethylenically unsaturated bond of 100 to 300 g / mol.

Description

Technical Field

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

[0002] Nowadays, in various fields, the technology of producing resin materials from resin compositions containing resins is being utilized.

[0003] For example, polyimide is used in various applications due to its excellent heat resistance and insulation properties. The above-mentioned applications are not particularly limited, and if semiconductor devices for mounting are used as an example, the use as an insulating film, a sealing material, or a protective film can be cited. In addition, it can also be used as a base film, a cover film, etc. of a flexible substrate.

[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] Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, subjected to exposure, development, heating, etc., to form a cured product on the substrate.

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

[0007] The resin composition can be applied by a known coating method, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, the applied resin composition has a high degree of freedom in designing the shape, size, application position, etc. during application. From the viewpoint of excellent adaptability in manufacturing in addition to the high performance of polyimide, the application development of the above-mentioned resin composition in industry is increasingly expected.

[0008] For example, Patent Document 1 describes a photosensitive resin composition comprising (A) 100 parts by mass of a polyimide precursor, (B) 0.1 to 10 parts by mass of a photosensitive agent, (C) 1 to 50 parts by mass of a low dielectric loss agent, and (D) 50 to 300 parts by mass of a solvent, wherein the molecular weight of the (C) low dielectric loss agent is 100 to 3,500.

[0009] Previous technical literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 2021-196482 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] With the miniaturization and high integration of devices, when a cured product is obtained from a resin composition containing at least one resin selected from polyimide and a polyimide precursor, it is required to obtain a fine pattern with excellent resolution.

[0014] The object of the present invention is to provide a resin composition having excellent resolution of the obtained cured product, a cured product formed by curing the above-mentioned resin composition, a laminate containing the above-mentioned cured product, a method for manufacturing the above-mentioned cured product, a method for manufacturing the above-mentioned laminate, a method for manufacturing a semiconductor device including the method for manufacturing the above-mentioned cured product, and a semiconductor device containing the above-mentioned cured product.

[0015] Means for solving technical problems

[0016] Hereinafter, examples of representative embodiments of the present invention will be described.

[0017] <1> A resin composition comprising:

[0018] At least one resin selected from polyimide and its precursor;

[0019] polymerizable compounds; and

[0020] Photopolymerization initiator,

[0021] The ethylenically unsaturated bond equivalent in the polymerizable compound is 100 to 300 g / mol.

[0022] <2> according to <1> The resin composition, wherein

[0023] The polymerizable compound is a polymerizable compound having two ethylenically unsaturated bonds.

[0024] <3> according to <1> The resin composition, wherein

[0025] The polymerizable compound is a di(meth)acrylate.

[0026] <4> according to <1> The resin composition, wherein

[0027] The above-mentioned polymerizable compound is a diacrylate.

[0028] <5> according to <1> The resin composition, wherein

[0029] The polymerizable compound is a compound containing a linear aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group and a polymerizable group.

[0030] <6> A resin composition comprising:

[0031] At least one resin selected from polyimide and its precursor;

[0032] A polymerizable compound represented by the following formula (1-1); and

[0033] Photopolymerization initiator.

[0034] [Chemical formula 1]

[0035]

[0036] When n is 1, L 1 represents a monovalent aliphatic hydrocarbon group in which a hydrogen atom may be substituted, and when n is 2 or more, L 1 represents an n-valent hydrocarbon group containing a structure represented by the following formula (L-1) in which the hydrogen atom may be substituted, or a structure represented by the following formula (L-2), R P represents a polymerizable group, n represents an integer greater than 1,

[0037] [Chemical formula 2]

[0038]

[0039] In formula (L-1), R L Each independently represents a hydrogen atom or a monovalent substituent, and * each independently represents a P The bonding position of the structure of , m represents an integer greater than 3, at least two of the m×2 RLs can be bonded to form a ring structure,

[0040] In formula (L-2), L Z1 and L Z2 Each independently represents a hydrocarbon group in which the hydrogen atom may be substituted, R each independently represents a substituent, a each independently represents an integer of 0 to 4, and * represents the same as R in formula (1-1). P bonding position.

[0041] <7> according to <6> The resin composition, wherein

[0042] The above L 1 It is a straight-chain or cyclic hydrocarbon group.

[0043] <8> according to <6> or <7> The resin composition, wherein

[0044] The above n is 2.

[0045] <9> according to <6> to <8> The resin composition described in any one of the preceding claims, wherein

[0046] The above R P It is a (meth)acryloyloxy group.

[0047] <10> according to <6> to <9> The resin composition described in any one of the preceding claims, wherein

[0048] The above L 1 It is an aliphatic hydrocarbon group.

[0049] <11> according to <1> to <10> The resin composition described in any one of the preceding claims, wherein

[0050] The resin has a group obtained by removing two or more hydrogen atoms from a structure represented by the following formula (A-1).

[0051] [Chemical formula 3]

[0052]

[0053] In formula (A-1), A 1 ~A 3 Each is independently a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

[0054] <12> according to <1> to <11> The resin composition described in any one of the preceding claims, wherein

[0055] The weight average molecular weight of the resin is 20,000 or less.

[0056] <13> according to <1> to <12> The resin composition described in any one of the preceding claims, wherein

[0057] The above resin is polyimide.

[0058] <14> according to <1> to <13> The resin composition according to any one of the preceding claims, further comprising a solvent,

[0059] The above-mentioned solvents include solvents containing a ketone structure.

[0060] <15> according to <1> to <14> The resin composition described above further comprises a light absorber.

[0061] <16> according to <15> The resin composition, wherein

[0062] The light absorber is naphthoquinone diazide.

[0063] <17> A solidified material, which is solidified <1> to <16> The resin composition described in any one of the above.

[0064] <18> according to <17> The dielectric loss tangent of the cured product at 28 GHz is less than 0.01.

[0065] <19> A laminate comprising two or more layers of <17> or <18> The layers are composed of the above-mentioned cured product, and a metal layer is included between any of the layers composed of the above-mentioned cured product.

[0066] <20> A method for producing a cured product, comprising applying a <1> to <16> A film forming step of forming a film using any one of the resin compositions.

[0067] <21> according to <20> The method for manufacturing the solidified material comprises:

[0068] An exposure step of selectively exposing the film; and

[0069] In the development step, the film is developed using a developer to form a pattern.

[0070] <22> according to <20> or <21> The method for producing the cured product comprises a heating step of heating the film at 50 to 450°C.

[0071] <23> A method for manufacturing a laminate, comprising: <20> to <22> The method for producing a cured product according to any one of the above.

[0072] <24> A method for manufacturing a semiconductor device, comprising: <20> to <22> The method for producing a cured product according to any one of the above.

[0073] <25> A semiconductor device comprising <17> or <18> The solidified material.

[0074] Effects of the Invention

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

[0076] Figure 1 is a schematic cross-sectional view of a test vehicle used in a biased HAST test. DETAILED DESCRIPTION

[0077] Hereinafter, the main embodiments of the present invention will be described. In addition, the present invention is not limited to the embodiments explicitly described.

[0078] In the present specification, a numerical range expressed by the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0079] In the present specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0080] In the marking of groups (atomic groups) in this specification, the marking not marked with substitution and unsubstituted includes groups (atomic groups) without substitution and also includes 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).

[0081] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, and electron beams.

[0082] In this specification, “(meth)acrylate” means both or either of “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either of “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0083] 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.

[0084] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components excluding the solvent relative to the total mass of the composition.

[0085] In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) method, defined as polystyrene conversion value. In this specification, for example, using HLC-8220GPC (TOSOH CORPORATION system), protective column HZ-L, TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as a column, thereby being able to obtain weight average molecular weight (Mw) and number average molecular weight (Mn). Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as eluent. And, unless otherwise specified, the detection in the GPC determination uses a UV ray (ultraviolet) detector with a wavelength of 254nm.

[0086] In this specification, when the positional relationship of each layer constituting the laminate is recorded as "up" or "down", as long as there are other layers on the upper side or lower side of the layer that becomes the reference in the multiple layers concerned. That is, the third layer or the third element can be further sandwiched between the layer that becomes the reference and the above-mentioned other layers, and the layer that becomes the reference does not need to contact the above-mentioned other layers. Unless otherwise specified, the direction of the substrate stacking layer is referred to as "up", or, when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of this up and down direction is for the convenience of explaining this specification, and in a practical manner, the "up" direction in this specification is also likely to be different from the vertical upward direction.

[0087] In this specification, as each component contained in the composition, the composition may contain two or more compounds belonging to the component unless otherwise specified. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to the component.

[0088] 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.

[0089] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0090] (Resin composition)

[0091] The resin composition according to the first aspect of the present invention (hereinafter also referred to as "first resin composition") comprises: at least one resin selected from polyimide and its precursor; a polymerizable compound; and a photopolymerization initiator.

[0092] The ethylenically unsaturated bond equivalent in the polymerizable compound is 100 to 300 g / mol.

[0093] The resin composition according to the second aspect of the present invention (hereinafter also simply referred to as “second resin composition”) contains: at least one resin selected from polyimide and its precursor; a polymerizable compound represented by the above formula (1-1); and a photopolymerization initiator.

[0094] Hereinafter, the first resin composition and the second resin composition are also simply collectively referred to as “resin composition”.

[0095] Hereinafter, the polymerizable compound having an ethylenically unsaturated bond equivalent of 100 to 300 g / mol contained in the first resin composition is also referred to as a "first specific polymerizable compound."

[0096] Hereinafter, the polymerizable compound represented by formula (1-1) contained in the second resin composition is also referred to as a "second specific polymerizable compound".

[0097] Hereinafter, when simply described as "specific polymerizable compound", it means all compounds corresponding to any one of the first specific polymerizable compound and the second specific polymerizable compound.

[0098] The resin composition of the present invention is preferably used to form a photosensitive film to be exposed and developed, and is preferably used to form a film to be exposed and developed using a developer containing an organic solvent.

[0099] 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, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.

[0100] In particular, it is also one of the preferred embodiments of the present invention that the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer.

[0101] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development.

[0102] In the present invention, negative-tone development refers to development in which non-exposed portions are removed by development during exposure and development, and positive-tone development refers to development in which exposed portions are removed by development.

[0103] As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product to be described later, and the developer and the development method described in the development step can be used.

[0104] According to the resin composition of the present invention, a cured product having excellent resolution can be obtained.

[0105] The mechanism by which the above effects are achieved is not yet clear, but is speculated as follows.

[0106] The resin composition according to the first aspect of the present invention comprises: at least one resin selected from polyimide and its precursor; a polymerizable compound; and a photopolymerization initiator.

[0107] The ethylenically unsaturated bond equivalent in the polymerizable compound is 100 to 300 g / mol.

[0108] The resin composition according to the second aspect of the present invention contains: at least one resin selected from polyimide and a precursor thereof; a polymerizable compound represented by formula (1-1); and a photopolymerization initiator.

[0109] Conventionally, a resin composition containing polyimide or a polyimide precursor contains a photopolymerization initiator and a polymerizable compound, and is exposed and developed to form a pattern.

[0110] Here, in recent years, due to the need for miniaturization and high integration of devices, higher resolution is required during pattern formation.

[0111] Here, the ethylenically unsaturated bond equivalent of the polymerizable compound involved in the first embodiment is 100 to 300 g / mol. It is believed that when the ethylenically unsaturated bond equivalent is 100 g / mol or more, the mobility of the molecule becomes high and the polymerization reaction is easy to proceed. In addition, when it is 300 g / mol or less, the density of the reaction points in the film becomes large and the reactivity is excellent.

[0112] The polymerizable compound according to the second embodiment includes a polymerizable compound represented by formula (1-1). 1 It is an aliphatic hydrocarbon group or contains a structure represented by the formula (L-1) or a structure represented by the following formula (L-2). It is considered that this can make the molecular weight between the polymerizable groups in the polymerizable compound relatively small and the reactivity excellent.

[0113] As described above, the resin composition of the present invention contains a polymerizable compound having excellent reactivity, so that polymerization in the exposed portion is easily carried out, and the difference in solubility in a developer between the exposed portion and the non-exposed portion becomes large, so it is considered that the resolution is excellent.

[0114] Here, Patent Document 1 does not describe an embodiment containing a polymerizable compound having an ethylenically unsaturated bond equivalent of 100 to 300 g / mol and an embodiment containing a polymerizable compound represented by formula (1-1).

[0115] Hereinafter, the physical properties of the resin composition of the present invention and the components contained in the resin composition of the present invention will be described in detail.

[0116] <Specific resin>

[0117] The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide and a precursor thereof.

[0118] The dielectric loss tangent (tan δ) of the specific resin is preferably less than 0.020, more preferably less than 0.015, further preferably less than 0.010, and particularly preferably less than 0.005.

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

[0120] The details of the method for measuring tan δ of the above-mentioned specific resin can be carried out by the method described in Examples below.

[0121] Furthermore, for example, when a plurality of resins are included as the specific resin, the dielectric loss tangent of at least one of the resins may be within the above range. Furthermore, it is also one of the preferred embodiments of the present invention that the dielectric loss tangent of all of the plurality of resins is within the above range.

[0122] Here, the content of the resin having a dielectric loss tangent within the above range relative to the total mass of the specific resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. The upper limit of the above content is not particularly limited, and 100% by mass is also one of the preferred embodiments of the present invention.

[0123] From the viewpoint of reliability, the resin composition of the present invention preferably contains polyimide as a specific resin. Reliability refers to the property of not being easily degraded over a long period of time and exerting the required performance such as insulation and adhesion over a long period of time, and especially refers to the property of exerting the required performance such as insulation and adhesion even after accelerated tests such as under high temperature and high humidity conditions.

[0124] From the viewpoint of resolution, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0125] 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 contains a free radical polymerization initiator and contains a free radical crosslinking agent. In addition, a sensitizer can be contained as needed. For example, a negative photosensitive film is formed from such a resin composition.

[0126] Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetanyl, benzoxazolyl, blocked isocyanate, and amino groups. As the radical polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.

[0127] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. Preferably, it is a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, and more preferably, a vinylphenyl group.

[0128] The polymerizable group value in the specific resin (the total molar amount of the polymerizable groups per 1 g of the specific resin) is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0129] The specific resin preferably has a group formed by removing two or more hydrogen atoms from a structure represented by the following formula (A-1), and more preferably has a group formed by removing two or more hydrogen atoms from a structure represented by the following formula (A-2).

[0130] [Chemical formula 4]

[0131]

[0132] In formula (A-1), A 1 ~A 3 Each is independently a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

[0133] A 1 ~A 3 Preferred are aliphatic hydrocarbon groups 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 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, further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms or -O-.

[0134] In particular, A 1 and A 3 Preferred is -O-.

[0135] 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.

[0136] Among them, A 1 and A 3 For -O- and A 2 -C(CH 3 )2 -mode is also one of the preferred modes of the present invention.

[0137] 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, and more preferably 1 to 4.

[0138] Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 - etc., among which -C(CH 3 ) 2 -.

[0139] Examples of the substituents on the four benzene rings described in the formula (A-1) include fluorine atoms and hydrocarbon groups having 1 to 10 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms.

[0140] Furthermore, an embodiment in which all four benzene rings described in formula (A-1) are unsubstituted is also one of the preferred embodiments of the present invention.

[0141] Furthermore, the specific resin preferably contains a structure represented by formula (A-1) as R in formula (2) described later. 115 or R 111 These methods will be described later.

[0142] Specific examples of the structure represented by formula (A-1) are described below, but the present invention is not limited to these.

[0143] [Chemical formula 5]

[0144]

[0145] Furthermore, from the viewpoint of resolution, an embodiment in which the weight average molecular weight of the specific resin is 20,000 or less is also one of the preferred embodiments of the present invention.

[0146] By adopting this method, it is easy to cause reflow during the heating process, so the flatness is excellent and the solubility of the resin composition in the developer is excellent, so it is believed that the resolution of the obtained cured product is excellent. Reflow refers to softening and flowing the film by heating, etc., which has the advantage of averaging the unevenness of the film surface.

[0147] The weight average molecular weight is preferably 17,000 or less, more preferably 13,000 or less, and further preferably 10,000 or less.

[0148] The lower limit of the weight average molecular weight is not particularly limited, but is preferably 5,000 or more.

[0149] 〔Polyimide precursor〕

[0150] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2).

[0151] [Chemical formula 6]

[0152]

[0153] 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.

[0154] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR Z -, preferably an oxygen atom.

[0155] R in formula (2) 111 Represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. Preferably, it is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. More preferably, it is a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group in the ring of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As R in formula (2) 111 Examples of the group include -Ar- and -Ar-L-Ar-, preferably -Ar-L-Ar-. Ar is independently an aromatic group, 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-, -SO 2 - or -NHCO- or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

[0156] R 111It 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.

[0157] 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 group consisting of a combination thereof, and more preferably diamines containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group in the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. Examples of the group containing an aromatic group include the following groups.

[0158] [Chemical formula 7]

[0159]

[0160] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO 2 -, -NHCO- or a combination thereof, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S- or -SO 2 - is more preferably -CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C(CH 3 ) 2 -.

[0161] In the formula, * indicates the bonding position with other structures.

[0162] As the diamine, specifically, there can be mentioned one selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane;

[0163] 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;

[0164] m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'- or 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis( 3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1, 3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'- dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, ethoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4 , at least one diamine selected from 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'-hexafluorotoluidine and 4,4'-diaminoquaterphenyl. ,

[0165] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0166] 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.

[0167] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-, wherein Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO- or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 The aliphatic hydrocarbon group here is preferably an alkylene group.

[0168] 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.

[0169] Formula (51)

[0170] [Chemical formula 8]

[0171]

[0172] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to a nitrogen atom in formula (2).

[0173] 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).

[0174] [Chemical formula 9]

[0175]

[0176] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to a nitrogen atom in formula (2).

[0177] Examples of the diamine that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0178] And, R 111 Also preferred is a group represented by the following formula (71). 111 More preferred is a group represented by the following formula (72).

[0179] Formula (71) is a group formed by removing two hydrogen atoms from the structure represented by the above formula (A-1), and formula (72) is a group formed by removing two hydrogen atoms from the structure represented by the above formula (A-2).

[0180] [Chemical formula 10]

[0181]

[0182] In formula (71), A 1 ~A 3Each independently represents a single bond or a divalent linking group, * represents the bonding position to the nitrogen atom in formula (2), and the four benzene rings described in formula (71) may each have a substituent.

[0183] In formula (72), * represents the bonding position to the nitrogen atom in formula (2).

[0184] In formula (71), A 1 ~A 3 and the preferred embodiment of the substituent in the benzene ring is the same as A in the above formula (A-1) 1 ~A 3 The same is true for the preferred embodiments of the substituents on the benzene ring.

[0185] And, R 111 Also preferred is a group represented by the following formula (81). 111 More preferred is a group represented by the following formula (82).

[0186] [Chemical formula 11]

[0187]

[0188] In formula (81), A 4 and A 5 Each independently represents a single bond or a divalent linking group, * represents the bonding position to the nitrogen atom in formula (2), and the three benzene rings described in formula (81) may each have a substituent.

[0189] In formula (82), * represents the bonding position to the nitrogen atom in formula (2).

[0190] In formula (81), A 4 and A 5 Each of them is independently preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)- 2 -, -NHC(=O)-, or a group consisting of a combination of two or more thereof, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more thereof, further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-, and particularly preferably -C(CH 3 ) 2 -.

[0191] 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 (6).

[0192] In formula (5) or (6), * independently represents a bonding position to another structure.

[0193] [Chemical formula 12]

[0194]

[0195] In formula (5), R 112 is a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - and -NHCO-, and groups in combination thereof, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO 2 -, further preferably selected from -CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 - is a divalent group.

[0196] And, R 115 Also preferably, it is a group represented by the following formula (7). 115 More preferred is a group represented by the following formula (7-2).

[0197] Formula (7) is a group formed by removing four hydrogen atoms from the structure represented by the above formula (A-1), and formula (7-2) is a group formed by removing four hydrogen atoms from the structure represented by the above formula (A-2).

[0198] [Chemical formula 13]

[0199]

[0200] In formula (7), A 1 ~A 3 Each of them is independently a single bond or a divalent linking group, * represents the bonding position to the carbonyl group in formula (2), and the four benzene rings described in formula (7) may each have a substituent.

[0201] In the present specification, a bond intersecting the side of a ring structure means a bond that replaces any of the hydrogen atoms in the ring structure.

[0202] In formula (7-2), * represents a bonding position to the carbonyl group in formula (2).

[0203] In formula (7), A 1 ~A 3and the preferred embodiment of the substituent in the benzene ring is the same as A in the above formula (A-1) 1 ~A 3 The same is true for the preferred embodiments of the substituents on the benzene ring.

[0204] About R 115 Specifically, the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride can be cited. 115 The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues.

[0205] Tetracarboxylic dianhydride is preferably represented by the following formula (0).

[0206] [Chemical formula 14]

[0207]

[0208] In formula (0), R 115 represents a tetravalent organic group. 116 The preferred range of is the same as that of R in formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0209] 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 derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0210] 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.

[0211] In formula (2), R 111 and R 115 At least one of R may have an OH group. 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0212] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114 At least one of them contains 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 methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0213] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferably, the group represented by the following formula (III) is included.

[0214] [Chemical formula 15]

[0215]

[0216] In formula (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0217] In formula (III), * indicates a bonding position with other structures.

[0218] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2-, cycloalkylene or polyalkyleneoxy.

[0219] Preferred R 201 Examples of alkylene groups include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy, more preferably alkylene such as ethylene and propylene, -CH 2 CH(OH)CH 2 -, cyclohexyl, or polyalkyleneoxy, and more preferably, an alkylene group or polyalkyleneoxy such as ethylene or propylene.

[0220] In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0221] When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0222] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0223] 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.

[0224] Furthermore, the number of the alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.

[0225] As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and further preferably a polyethyleneoxy group. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0226] In formula (2), in R 113 In the case of a hydrogen atom or R 114When 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.

[0227] 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.

[0228] 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.

[0229] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By containing a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased.

[0230] Formula (2-A)

[0231] [Chemical formula 16]

[0232]

[0233] 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.

[0234] A 1 , A 2 , R 111 , R 113 and R 114 and A in formula (2) independently. 1 , A 2 , R 111 , R 113 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0235] R 112 With R in formula (5)112 The meanings are the same, and the preferred ranges are also the same.

[0236] Furthermore, the polyimide precursor also preferably contains a repeating unit represented by the following formula (1-2) as the repeating unit represented by the formula (2).

[0237] [Chemical formula 17]

[0238]

[0239] In formula (1-2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group, m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0240] [Chemical formula 18]

[0241]

[0242] In formula (R-1), L 1 represents a2+1 valent connecting group, A 1 represents a polymerizable group, a2 represents an integer greater than 1, and * represents the same as X in formula (1-2). 1 or Y 1 bonding position.

[0243] X in formula (1-2) 1 , Y 1 , R 1 The preferred embodiments of n and m are the same as those of X in the formula (4-3) described later. 1 , Y 1 , R 1 The preferred embodiments of , n and m are the same.

[0244] A in formula (1-2) 1 , A 2 , R 113 and R 114 The preferred embodiment is the same as A in the above formula (2) 1 , A 2 , R 113 and R 114 The preferred method is the same.

[0245] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, the polyimide precursor 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 contain other types of repeating units.

[0246] As one embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by formula (2) can be cited as 50 mol% or more of all repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, except that all repeating units in the polyimide precursor at the end can be repeating units represented by formula (2).

[0247] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, and further preferably 7,000 to 20,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 20,000, and further preferably 4,000 to 10,000.

[0248] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0249] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0250] 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 dispersion degree of at least one polyimide precursor are within the above ranges. In addition, the weight average molecular weight, number average molecular weight and dispersion degree calculated by taking the multiple polyimide precursors as one resin are preferably within the above ranges, respectively.

[0251] 〔Polyimide〕

[0252] 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.

[0253] In this specification, the 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., preferably 0.5 g or more, and more preferably 1.0 g or more from the viewpoint of pattern formation. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0254] From the viewpoint of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0255] -Fluorine atom-

[0256] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has fluorine atoms.

[0257] 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 below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a fluorinated alkyl group is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0258] 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.

[0259] -Silicon Atoms-

[0260] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has a silicon atom.

[0261] The silicon atom is preferably present in R in the repeating unit represented by the formula (4) described below. 131 Among them, R in the repeating unit represented by the formula (4) described below is more preferably included as the organo-modified (poly)siloxane structure described below. 131 middle.

[0262] 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.

[0263] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0264] -Ethylenically unsaturated bond-

[0265] From the viewpoint of film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0266] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or at a side chain, and preferably has an ethylenically unsaturated bond at a side chain.

[0267] The ethylenically unsaturated bond preferably has radical polymerizability.

[0268] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 It is more preferred that the group having an ethylenically unsaturated bond is contained in R 132 or R 131 middle.

[0269] Among them, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 It is more preferred that the group having an ethylenically unsaturated bond is contained in R 131 middle.

[0270] Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0271] [Chemical formula 19]

[0272]

[0273] In formula (IV), R 20 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0274] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -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 two or more thereof.

[0275] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or combinations thereof.

[0276] 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.

[0277] Among them, R21 The group is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0278] [Chemical formula 20]

[0279]

[0280] In formulas (R1) to (R3), L represents a single bond or 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 them, X represents an oxygen atom or a sulfur atom, * represents a bonding position with other structures, and ● represents the bonding position with R in formula (IV). 21 The bonding position of the bonded oxygen atom.

[0281] In formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as that of R in formula (IV). 21 The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.

[0282] In formula (R1), X is preferably an oxygen atom.

[0283] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same.

[0284] 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).

[0285] The structure represented by the formula (R2) can be obtained, for example, 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).

[0286] The structure represented by the formula (R3) can be obtained by, for example, 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).

[0287] In formula (IV), * represents a bonding position to other structures, and is preferably a bonding position to the main chain of the polyimide.

[0288] The amount of the ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0289] -Polymerizable groups other than groups having ethylenically unsaturated bonds-

[0290] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0291] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0292] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained in, for example, R 131 middle.

[0293] 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, based on the total mass of the polyimide.

[0294] -Acid value-

[0295] When the polyimide is used for alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0296] 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.

[0297] When the polyimide is used for development using a developer containing an organic solvent as the main component (eg, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0298] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0299] 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.

[0300] pKa is a value that takes into account the dissociation reaction of releasing hydrogen ions from an acid and represents its equilibrium constant Ka by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD / ChemSketch (registered trademark). pKa can refer to the values ​​recorded in "Revised 5th Edition of Chemistry Handbook Basics" compiled by the Chemical Society of Japan.

[0301] When the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0302] 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.

[0303] -Phenolic hydroxyl group-

[0304] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0305] The polyimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group in a side chain.

[0306] 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.

[0307] The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0308] 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).

[0309] [Chemical formula 21]

[0310]

[0311] In formula (4), R 131 Represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0312] Here, the repeating unit represented by formula (4) may have one of the imide structures open as in the structure represented by the following formula (4-A). In the structure represented by formula (4-A), the left side of the two imide rings is open, but the right side may also be open. In the following, in formula (4-1), formula (4-2), and formula (4-3), one of the imide structures may also be open.

[0313] [Chemical formula 22]

[0314]

[0315] In formula (4-A), R 131 Represents a divalent organic group, R 132 Represents a 4-valent organic group, A 1 Represents oxygen atom or -NR z-, R 114 represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0316] In formula (4-A), R 131 and R 132 The preferred embodiment is the same as R in formula (4) 131 and R 132 The preferred method is the same.

[0317] In formula (4-A), A 1 and R 114 The preferred embodiment is the same as A in formula (2) 1 and R 114 The preferred method is the same.

[0318] 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).

[0319] Formula (4-1)

[0320] [Chemical formula 23]

[0321]

[0322] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0323] Formula (4-2)

[0324] [Chemical formula 24]

[0325]

[0326] 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).

[0327] Examples of the polymerizable group include the above-mentioned ethylenically unsaturated bond-containing group and the above-mentioned crosslinkable group other than the group having an ethylenically unsaturated bond.

[0328] R 131 The divalent organic group includes the following: 111 The preferred ranges are the same.

[0329] As R 131, and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 Example.

[0330] From the viewpoint of more effectively suppressing the warping during calcination, R 131 Preferably, the diamine residue has at least two alkylene glycol units in the main chain. More preferably, the diamine residue contains two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule. Still more preferably, the diamine residue contains no aromatic ring.

[0331] Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

[0332] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include 115 The preferred ranges are the same.

[0333] For example, as R 115 The four bonding groups of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the formula (4) to form a condensed ring.

[0334] 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.

[0335] 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 R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0336] Furthermore, the polyimide also preferably contains a repeating unit represented by the following formula (4-3) as the repeating unit represented by the formula (4).

[0337] [Chemical formula 25]

[0338]

[0339] In formula (4-3), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group with 4 or more carbon atoms, R 1 Each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or greater.

[0340] [Chemical formula 26]

[0341]

[0342] In formula (R-1), L 1 represents a2+1 valent connecting group, A 1 represents a polymerizable group, a2 represents an integer greater than 1, and * represents the same as X in formula (4-3). 1 or Y 1 bonding position.

[0343] -R 1 -

[0344] R 1 Each independently represents the structure represented by formula (R-1).

[0345] In formula (R-1), L 1 It represents a2+1 valent connecting group.

[0346] L 1 Preferred is a group represented by the following formula (LR-1).

[0347] [Chemical formula 27]

[0348]

[0349] In formula (LR-1), L xrepresents an a2+1 valent linking group, a2 represents an integer greater than 1, and * represents the same as X in formula (4-3) 1 or Y 1 The bonding position of A in formula (R-1) is indicated by #. 1 bonding position.

[0350] L x An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0351] Preferred aspects of a2 in formula (LR-1) are the same as preferred aspects of a2 in formula (R-1).

[0352] -A 1 -

[0353] A in formula (R-1) 1 represents a polymerizable group, and preferred embodiments of the polymerizable group are the same as preferred embodiments of the polymerizable group in the above-mentioned specific resin.

[0354] Among them, A in formula (R-1) contained in formula (4-3) 1 At least one of the groups is preferably a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, and more preferably a vinylphenyl group.

[0355] -a2-

[0356] In the formula (R-1), a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0357] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0358] -X 1 -

[0359] In formula (4-3), X 1 It preferably contains a structure in which two or more hydrogen atoms are removed from a structure represented by any one of the following formulae (V-1) to (V-4).

[0360] [Chemical formula 28]

[0361]

[0362] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0363] In formula (V-3), R X2 and R X3 Each independently represents a hydrogen atom or a substituent, R X2With R X3 They may be bonded to form a ring structure.

[0364] In formula (V-2), R X1 Each of them is independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one of the hydrogen atoms of the alkyl group is substituted by a halogen atom. As the halogen atom, F or C1 is preferred, and F is more preferred.

[0365] In formula (V-3), R X2 and R X3 Each independently is preferably a hydrogen atom.

[0366] In R X2 With R X3 When the two are bonded to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -CR 2 -, more preferably -O- or -CR 2 -, more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0367] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1): In the following formula, * represents the same group as X in formula (4-3). 1 The bonding positions of the four bonded carbonyl groups, n1 represents an integer of 0 to 5, and is preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms be substituted with R in the formula (4-3). 1 replace.

[0368] [Chemical formula 29]

[0369]

[0370] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), X is preferably 1 It is a group represented by the following formula (V-2-1) or formula (V-2-2), and is preferably a group represented by formula (V-2-2) from the viewpoint of reducing the amine value in the resin. X1represents a single bond or -O-, and * represents the X in formula (4-3) 1 The bonding positions of the four carbonyl groups bonded. X1 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (4-3). 1 replace.

[0371] [Chemical formula 30]

[0372]

[0373] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X is preferably 1 It is a group represented by the following formula (V-3-1) or formula (V-3-2), and is preferably a group represented by formula (V-3-2) from the viewpoint of lowering the dielectric constant. In the following formula, * represents the same as X in formula (4-3). 1 The bonding positions of the four carbonyl groups bonded to the carbonyl groups. X2 and R X3 The definition and preferred embodiment of are as described above. In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (4-3). 1 replace.

[0374] [Chemical formula 31]

[0375]

[0376] In X 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X is preferably 1 is a group represented by the following formula (V-4-1). In the following formula, * represents the same as X in formula (4-3). 1 The bonding positions of the four carbonyl groups bonded, and n1 represents an integer of 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group or a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer of 1 to 4, it is preferred that m hydrogen atoms are substituted by R in the formula (4-3). 1 replace.

[0377] [Chemical formula 32]

[0378]

[0379] In addition, X 1 It can be R in the above formula (4) 132 The group represented by is obtained by removing m hydrogen atoms.

[0380] And, X 1 It is preferred that no imide structure be contained in the structure.

[0381] In the present invention, the imide structure is a structure represented by -C(=0)N(-*)C(=0)-. * represents a bonding position to another structure.

[0382] And, X 1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0383] In the present invention, the urethane bond refers to the bond consisting of *-OC(=O)-NR N -* indicates a key, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N It is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

[0384] In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N R and R each independently represent a hydrogen atom or a monovalent organic group, and * each represents a bonding position to a carbon atom. N The preferred manner is as described above.

[0385] In the present invention, the amide bond is composed of *-NR N -C(=O)-* represents a bond, R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to the carbon atom. N The preferred manner is as described above.

[0386] In addition, X 1 It is preferred that no ester bond is contained in the structure.

[0387] In the present invention, the ester bond is a bond represented by *-OC(=O)-*.

[0388] Among them, X 1 It is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, and no amide bond, and it is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, no amide bond, and no ester bond.

[0389] -Y 1 -

[0390] In formula (4-3), Y 1It is preferably a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of the above formulae (V-1) to (V-4).

[0391] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y is preferably 1 It is a group formed by removing n hydrogen atoms from the group represented by the following formula (V-1-2). In the following formula, * represents the same as Y in formula (4-3). 1 The bonding positions of the two nitrogen atoms to be bonded, and n1 represents an integer of 1 to 5. In the following structure, n of the hydrogen atoms are replaced by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0392] [Chemical formula 33]

[0393]

[0394] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y is preferably 1 It is a group represented by the following formula (V-2-3) or formula (V-2-4), and is preferably a group represented by formula (V-2-4) from the viewpoint of lowering the dielectric constant. X1 represents a single bond or -O-, and * represents the same as Y in formula (4-3) 1 The bonding positions of the two nitrogen atoms to which R X1 The preferred embodiment is as described above. In the following structure, n hydrogen atoms are replaced by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0395] [Chemical formula 34]

[0396]

[0397] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y is preferably 1 It is a group represented by the following formula (V-3-3) or formula (V-3-4), and is preferably a group represented by formula (V-3-3) from the viewpoint of lowering the dielectric constant. In the following formula, * represents the same as Y in formula (4-3). 1The bonding positions of the two nitrogen atoms to which R X2 and R X3 The preferred embodiment is as described above. In the following structure, n hydrogen atoms are replaced by R in formula (4-3). 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0398] [Chemical formula 35]

[0399]

[0400] In Y 1 In the case of a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y is preferably 1 is a group represented by the following formula (V-4-2). In the following formula, * represents the same as Y in formula (4-3). 1 The bonding positions of the two nitrogen atoms bonded are as follows: n1 represents an integer of 0 to 5. Furthermore, the embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. 1 The meaning of n is the same as that of n in formula (4-3). In addition, the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxyl group or a hydrocarbon group.

[0401] [Chemical formula 36]

[0402]

[0403] In addition, Y 1 It can be R in the above formula (4) 131 The group represented by is obtained by removing n hydrogen atoms.

[0404] And, Y 1 It is preferred that no imide structure be contained in the structure.

[0405] And, Y 1 It is preferred that the structure does not contain a urethane bond, a urea bond, or an amide bond.

[0406] In addition, Y 1 Preferably, there are no ester bonds in the structure.

[0407] Among them, Y 1 It is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, and no amide bond, and it is preferred that the polyol contains no imide structure, no urethane bond, no urea bond, no amide bond, and no ester bond.

[0408] Among them, X in formula (4-3) 1 and Y 1Each preferably contains a structure in which two or more hydrogen atoms are removed from the structure represented by any one of the above formulae (V-1) to (V-4).

[0409] In formula (4-3), m is preferably an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which m is 0 is also one of the preferred embodiments of the present invention.

[0410] In formula (4-3), n is preferably 1 or 2, and more preferably 2.

[0411] 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.

[0412] In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

[0413] In order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably capped by a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or a monoactive ester compound. Among them, monoamine is more preferably used, and 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, Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0414] -Imidization rate (ring closure rate)-

[0415] 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 more, more preferably 80% or more, and even more preferably 90% or more.

[0416] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0417] The imidization ratio can be measured, for example, by the following method.

[0418] The infrared absorption spectrum of polyimide was measured and the absorption peak at 1377 cm-1 derived from the imide structure was found. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to obtain the peak intensity P1 at 1377 em. -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0419] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0420] Polyimide may contain repeating units with all R 131 and R 132 The repeating unit represented by the above formula (4) may also contain R 131 and R 132 The polyimide may contain 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, repeating units represented by the following formula (2) can be cited.

[0421] Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with diamine (a portion of which is substituted with a capping agent that is a monoamine) at low temperature; a method of reacting tetracarboxylic dianhydride (a portion of which is substituted with a capping agent that is an acid anhydride, a monoacyl chloride compound, or a monoactive ester compound) with diamine at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester with a diamine (a portion of which is substituted with a capping agent that is a monoamine) in the presence of a condensation agent; a method of obtaining a polyimide precursor by a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then chlorinating the remaining dicarboxylic acid and reacting the diester with a diamine (a portion of which is substituted with a capping agent that is a monoamine), and completely imidizing the diester using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a portion of an imide structure; and a method of introducing a portion of an imide structure by mixing a completely imidized polymer and the polyimide precursor. Furthermore, other known methods for synthesizing polyimide can also be applied.

[0422] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, and further preferably 7,000 to 20,000. The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 20,000, and further preferably 4,000 to 10,000.

[0423] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0424] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide are within the above ranges. The weight average molecular weight, number average molecular weight and dispersion degree calculated using the multiple polyimides as one resin are also preferably within the above ranges.

[0425] [Method for producing polyimide precursor, etc.]

[0426] For example, the polyimide precursor can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature, a method of reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid and esterifying with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester in the presence of a diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the remaining dicarboxylic acid with a diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the remaining dicarboxylic acid with a diamine is more preferred.

[0427] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0428] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.

[0429] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.

[0430] In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0431] The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0432] In the method for producing a polyimide precursor, etc., it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0433] The basic compound can be appropriately determined depending on the starting material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0434] -Capping agent-

[0435] In the manufacturing method of polyimide precursor etc., in order to further improve storage stability, it is preferred to seal the carboxylic anhydride, anhydride derivative or amino group remaining at the resin end of polyimide precursor etc. When the carboxylic anhydride and anhydride derivative remaining at the resin end are blocked, as the end-blocking agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be cited. From the perspective of reactivity and film stability, monoalcohol, phenols and monoamines are more preferably used. As the preferred compound of monoalcohol, primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as ... Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0436] Moreover, when the amino group at the end of the resin is blocked, it can be blocked with a compound having a functional group that can react with the amino group. The preferred blocking agent for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and more preferably carboxylic anhydride and carboxylic acid chloride. As the preferred compound of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be mentioned. And, as the preferred compound of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be mentioned.

[0437] -Solid Precipitation-

[0438] In the manufacture method of polyimide precursor etc., the process of solid precipitation can be included. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as required, the obtained polymer component is put into poor solvents such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, so that it can be precipitated with solid and dried to obtain polyimide precursor etc. In order to improve the degree of purification, operations such as redissolution, reprecipitation, precipitation, drying, etc. can be repeatedly performed to polyimide precursor etc. In addition, the process of using ion exchange resin to remove ionic impurities can also be included.

[0439] 〔content〕

[0440] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the resin composition.

[0441] 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.

[0442] The resin composition of the present invention also preferably contains at least two types of resins.

[0443] Specifically, the resin composition of the present invention may contain two or more specific resins in total of the specific resin and other resins described below, or may contain two or more specific resins, and preferably contains two or more specific resins.

[0444] When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains a structure derived from a dianhydride (R in the above formula (2) 115 ) Two or more different polyimide precursors.

[0445] <Other resins>

[0446] 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").

[0447] As other resins, other polyimide precursors different from the specific resin, polyimide, polybenzoxazole precursor, polybenzoxazole, polyamideimide precursor, polyamideimide, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. can be mentioned.

[0448] Examples of other polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above descriptions are incorporated into the present specification.

[0449] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0450] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0451] 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, relative to the total solid content of the resin composition, 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. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0452] 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.

[0453] <Specific polymerizable compound>

[0454] The first resin composition of the present invention contains a polymerizable compound (first specific polymerizable compound) having an ethylenically unsaturated bond equivalent of 100 to 300 g / mol.

[0455] [First specific polymerizable compound]

[0456] The ethylenic unsaturated bond equivalent refers to the molecular weight of the compound relative to the total molar amount of ethylenic unsaturated bonds (molecular weight / total molar amount of ethylenic unsaturated bonds).

[0457] The lower limit of the ethylenically unsaturated bond equivalent of the first specific polymerizable compound is preferably 110 g / mol or more, more preferably 120 g / mol or more, and further preferably 130 g / mol or more.

[0458] The upper limit of the ethylenically unsaturated bond equivalent of the first specific polymerizable compound is preferably 290 g / mol or less, more preferably 280 g / mol or less, and further preferably 270 g / mol or less.

[0459] In the first specific polymerizable compound, as a group having an ethylenically unsaturated bond, preferably contains a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (meth)acrylamide group or a (meth)acryloyloxy group, more preferably contains a (meth)acryloyloxy group, and further preferably contains an acryloyloxy group.

[0460] The first specific polymerizable compound is preferably a polymerizable compound having 1 to 4 ethylenically unsaturated bonds, more preferably a polymerizable compound having 1 or 2 ethylenically unsaturated bonds, and further preferably a polymerizable compound having 2 ethylenically unsaturated bonds from the viewpoint of resolution and chemical resistance.

[0461] The first specific polymerizable compound is preferably a mono(meth)acrylate or a di(meth)acrylate, and is more preferably a di(meth)acrylate from the viewpoint of resolution and chemical resistance.

[0462] Furthermore, the first specific polymerizable compound is preferably a monoacrylate or a diacrylate, and is more preferably a diacrylate from the viewpoint of resolution and chemical resistance.

[0463] The first specific polymerizable compound is preferably a compound containing a linear aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group and a polymerizable group, and is preferably a compound containing a linear aliphatic hydrocarbon group and a polymerizable group from the viewpoint of the dielectric loss tangent of the obtained cured product.

[0464] Preferred embodiments of the polymerizable group are the same as preferred embodiments of the group having the above-mentioned ethylenically unsaturated bond.

[0465] The linear aliphatic hydrocarbon group is preferably a linear aliphatic saturated hydrocarbon group.

[0466] From the viewpoint of resolution, the number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 5 or more, more preferably 6 or more, further preferably 9 or more, and more preferably 10 or more. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 20 or less, and more preferably 15 or less.

[0467] The hydrogen atoms in the above-mentioned aliphatic hydrocarbon group may be substituted with halogen atoms, etc. As the halogen atom, a fluorine atom is preferred. In addition, the embodiment in which the above-mentioned aliphatic hydrocarbon group is unsubstituted is also one of the preferred embodiments of the present invention.

[0468] The cyclic aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group.

[0469] The cyclic aliphatic hydrocarbon group may be a monocyclic ring or a polycyclic ring, and is preferably a condensed ring.

[0470] The cyclic aliphatic hydrocarbon group has preferably 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 6 to 12 carbon atoms.

[0471] Specific examples of the ring structure in the cyclic aliphatic hydrocarbon group include a tetrahydrodicyclopentadiene ring, a cyclohexane ring, an isobornene ring, a norbornene ring, and an adamantane ring.

[0472] Among them, from the viewpoint of dielectric loss tangent, the first specific polymerizable compound is preferably an alkyl mono(meth)acrylate or an alkylene di(meth)acrylate, and more preferably an alkylene di(meth)acrylate.

[0473] Furthermore, from the viewpoint of dielectric loss tangent, the first specific polymerizable compound is preferably an alkyl monoacrylate or an alkylene diacrylate, and more preferably an alkylene diacrylate.

[0474] Furthermore, the first specific polymerizable compound is also preferably a compound including a structure represented by the following formula (Z-1) and a polymerizable group.

[0475] [Chemical formula 37]

[0476]

[0477] In formula (Z-1), L Z1 and L Z2 Each independently represents a hydrocarbon group in which a hydrogen atom may be substituted, each R independently represents a substituent, each a independently represents an integer of 0 to 4, and * represents a bonding position to a polymerizable group.

[0478] In formula (Z-1), L Z1 and L Z2 Each of them is independently preferably an alkylene group in which a hydrogen atom may be substituted, and more preferably a straight-chain alkylene group in which a hydrogen atom may be substituted. Z1and L Z2 Each independently is preferably an unsubstituted alkylene group, and is also preferably an unsubstituted straight-chain alkylene group.

[0479] L Z1 and L Z2 The number of carbon atoms in is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0480] In the formula (Z-1), examples of R include an alkyl group, an aryl group, a halogen atom, and the like.

[0481] In formula (Z-1), a is preferably an integer of 0 to 2, and more preferably 0 or 1. Furthermore, an embodiment in which all a's are 0 is also one of the preferred embodiments of the present invention.

[0482] In formula (Z-1), * is preferably bonded to the polymerizable group via a single bond without a linking group.

[0483] The preferred embodiment of the polymerizable group is the same as the preferred embodiment of the group having the above-mentioned ethylenically unsaturated bond. Here, the polymerizable group is also preferably a (meth)acryloyloxy group or a vinyl group. In addition, in the above embodiment, the embodiment in which the polymerizable group is an acryloyloxy group is also one of the preferred embodiments of the present invention.

[0484] The first specific polymerizable compound is preferably a polymerizable compound represented by the following formula (1-1).

[0485] [Second specific polymerizable compound]

[0486] The second resin composition of the present invention contains a polymerizable compound (second specific polymerizable compound) represented by formula (1-1).

[0487] [Chemical formula 38]

[0488]

[0489] When n is 1, L 1 represents a monovalent aliphatic hydrocarbon group in which a hydrogen atom may be substituted, and when n is 2 or more, L 1 represents an n-valent hydrocarbon group containing a structure represented by the following formula (L-1) in which the hydrogen atom may be substituted, or a structure represented by the following formula (L-2), R P represents a polymerizable group, and n represents an integer of 1 or greater.

[0490] [Chemical formula 39]

[0491]

[0492] In formula (L-1), R LEach independently represents a hydrogen atom or a monovalent substituent, and * each independently represents a P wherein m represents an integer greater than or equal to 3, and at least two of the m×2 RLs may be bonded to form a ring structure.

[0493] In formula (L-2), L Z1 and L Z2 Each independently represents a hydrocarbon group in which the hydrogen atom may be substituted, R each independently represents a substituent, a each independently represents an integer of 0 to 4, and * represents the same as R in formula (1-1). P bonding position.

[0494] In formula (1-1), L 1 It is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group.

[0495] In formula (1-1), when n is 1, L 1 More preferred is an alkyl group in which a hydrogen atom may be substituted.

[0496] The alkyl group may be linear, branched, cyclic, or a combination thereof, and is preferably linear or branched, and more preferably branched from the viewpoint of solvent solubility.

[0497] The alkyl group has preferably 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms.

[0498] As a substituent for the above hydrogen atom, a halogen atom or the like can be mentioned. As the halogen atom, a fluorine atom is preferred. 1 An embodiment in which the hydrocarbon group is unsubstituted is also one of the preferred embodiments of the present invention.

[0499] In formula (1-1), when n is 2 or more and L 1 When L represents an n-valent hydrocarbon group containing a structure represented by formula (L-1) in which a hydrogen atom may be substituted, 1 It preferably represents an n-valent aliphatic hydrocarbon group containing a structure represented by formula (L-1) in which a hydrogen atom may be substituted, and more preferably represents an n-valent aliphatic saturated hydrocarbon group containing a structure represented by formula (L-1) in which a hydrogen atom may be substituted.

[0500] As a substituent for the above hydrogen atom, a halogen atom or the like can be mentioned. As the halogen atom, a fluorine atom is preferred. 1 An embodiment in which the hydrocarbon group is unsubstituted is also one of the preferred embodiments of the present invention.

[0501] Among them, in formula (1-1), L 1 A linear or cyclic hydrocarbon group is preferred.

[0502] As the linear hydrocarbon group, a linear aliphatic hydrocarbon group is preferred, and a linear aliphatic saturated hydrocarbon group is more preferred.

[0503] Preferred embodiments of the linear aliphatic saturated hydrocarbon group are the same as the preferred embodiments of the linear aliphatic saturated hydrocarbon group in the first specific polymerizable compound.

[0504] The cyclic hydrocarbon group is preferably a cyclic aliphatic hydrocarbon group, and more preferably a cyclic aliphatic saturated hydrocarbon group.

[0505] Preferred embodiments of the cyclic aliphatic saturated hydrocarbon group are the same as the preferred embodiments of the cyclic aliphatic saturated hydrocarbon group in the first specific polymerizable compound.

[0506] In formula (L-1), R L Each independently represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom. Examples of the monovalent substituent include an alkyl group and a halogen atom. As the halogen atom, a fluorine atom is preferred. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred.

[0507] As m×2 R L Examples of the ring structure formed by bonding at least two of the rings include a tetrahydrodicyclopentadiene ring, a cyclohexane ring, an isobornene ring, a norbornene ring, and an adamantane ring.

[0508] In formula (L-1), m is preferably an integer of 4 or more, more preferably an integer of 5 or more, further preferably an integer of 6 or more, and particularly preferably an integer of 9 or more. The upper limit of m is preferably 20 or less, more preferably 15 or less.

[0509] In formula (L-1), * represents the same as R in formula (1-1). P The bonding position of the structure is preferably not connected to the R in formula (1-1) by a single bond without a linking group. P The bonding position of the bond.

[0510] In formula (L-2), L Z1 , L Z2 The preferred embodiments of R and a are the same as those of L in the above formula (Z-1). Z1 , L Z2 The preferred embodiments of , R and a are the same.

[0511] In formula (1-1), in L 1 In the case of a structure represented by formula (L-2), n in formula (1-1) is 2.

[0512] In formula (L-2), * represents the same as R in formula (1-1). P The bonding position is not connected to the R in formula (1-1) by a single bond.P The bonding position of the bond.

[0513] In formula (1-1), when n is 1, or when n is 2 or more and L 1 In the case of an n-valent hydrocarbon group having a structure represented by formula (L-1) in which a hydrogen atom may be substituted, L 1 The formula weight is preferably 70-250, more preferably 100-200, further preferably 140-180.

[0514] In formula (1-1), when n is 2 or more and L 1 In the case of a structure represented by formula (L-2), L 1 The formula weight is preferably 370-600, more preferably 370-500, further preferably 370-450.

[0515] In formula (1-1), R P Preferred are vinyl, allyl, isoallyl, 2-methylallyl, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), (meth)acrylamide, or (meth)acryloyloxy. From the viewpoint of resolution and dielectric loss tangent, (meth)acryloyloxy is more preferred, and acryloyloxy is still more preferred.

[0516] In formula (1-1), n ​​is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.

[0517] The ethylenically unsaturated bond equivalent of the second specific polymerizable compound is preferably 100 to 300 g / mol.

[0518] The lower limit of the ethylenically unsaturated bond equivalent of the second specific polymerizable compound is preferably 110 g / mol or more, more preferably 120 g / mol or more, and further preferably 130 g / mol or more.

[0519] The upper limit of the ethylenically unsaturated bond equivalent of the second specific polymerizable compound is preferably 290 g / mol or less, more preferably 280 g / mol or less, and further preferably 270 g / mol or less.

[0520] 〔Molecular weight〕

[0521] The molecular weight of the specific polymerizable compound is preferably 120 to 600, more preferably 150 to 500, and even more preferably 180 to 400.

[0522] [Specific example]

[0523] Specific examples of the specific polymerizable compound include compounds used in Examples described below.

[0524] 〔content〕

[0525] The content of the specific polymerizable compound is preferably 5 to 40% by mass, more preferably 6 to 35% by mass, and even more preferably 7 to 30% by mass, based on the total solid content of the resin composition of the present invention.

[0526] The specific polymerizable compound 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.

[0527] <Other polymerizable compounds>

[0528] The resin composition of the present invention preferably contains other polymerizable compounds.

[0529] Other polymerizable compounds are compounds that do not correspond to the above-mentioned specific polymerizable compounds.

[0530] Examples of other polymerizable compounds include radical crosslinking agents and other crosslinking agents.

[0531] 〔Free radical crosslinking agent〕

[0532] The resin composition of the present invention may contain a radical crosslinking agent.

[0533] 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 above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be cited.

[0534] 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.

[0535] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0536] As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenically unsaturated bonds is further preferred.

[0537] 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.

[0538] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0539] As a specific example of a free radical crosslinking agent, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, thiols and addition reaction products of monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids can also be preferably used. In addition, unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups and epoxy groups and addition reaction products of monofunctional or polyfunctional alcohols, amines, and thiols are preferably used, and further unsaturated carboxylic acid esters or amides with dissociable substituents such as halogen groups, tosyloxy groups and substitution reaction products of monofunctional or polyfunctional alcohols, amines, and thiols are also preferably used. In addition, as another example, the above unsaturated carboxylic acid may be replaced with a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinylbenzene, or an allyl ether. As a specific example, reference may be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein.

[0540] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of the compound having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189, etc. This content is incorporated into this specification.

[0541] Preferred radical crosslinking agents other than those described above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, etc. The contents are incorporated into the present specification.

[0542] As the radical crosslinking agent, dipentaerythritol tetraacrylate (commercially available products are KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products are KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which (meth)acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0543] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0544] The free radical crosslinking agent may be a free radical crosslinking agent 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 polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a free radical crosslinking agent having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Particularly preferred are the following compounds: in the free radical crosslinking agent having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

[0545] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and more preferably 1 to 100 mgKOH / g. As long as the acid value of the radical crosslinking agent is within the above range, the workability in production and the developability are excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

[0546] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition.

[0547] As specific compounds, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified dimethacrylate, bifunctional acrylates with other urethane bonds, and bifunctional methacrylates with urethane bonds can be used. Two or more of these can be mixed and used as needed.

[0548] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200.

[0549] 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 the monofunctional radical crosslinking agent, (meth)acrylic acid derivatives such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate can be preferably used. As the 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.

[0550] When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the resin composition. The lower limit is more preferably more than 5% by mass. The upper limit is more preferably less than 50% by mass, and further preferably less than 30% by mass.

[0551] 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.

[0552] 〔Other cross-linking agents〕

[0553] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0554] The other crosslinking agent refers to a crosslinking agent other than the above-mentioned free radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0555] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0556] As other crosslinking agents, compounds having at least one group selected from acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0557] As other crosslinking agents, for example, compounds having the following structure can be cited: a structure in which an amino-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, benzoguanamine, etc. is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. They may be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[0558] As the above-mentioned amino-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.

[0559] Among them, the resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0560] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of a urea structure described below, or on a triazine.

[0561] The alkoxymethyl group or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms.

[0562] The total number of the alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0563] The molecular weight of the compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0564] [Chemical formula 40]

[0565]

[0566] R 100 represents an alkyl group or an acyl group.

[0567] R 101 and R 102 Each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0568] Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with an aromatic group include compounds represented by the following general formula.

[0569] [Chemical formula 41]

[0570]

[0571] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, -C(R 4 ) 2 COOR 5 The group represented by (R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 It represents a group that is released by the action of an acid.

[0572] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0573] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that leaves by the action of an acid, -C(R 4 ) 2 COOR5 R in the group represented 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0574] In the formula, R 36 ~R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0575] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0576] The above-mentioned alkyl group may be either linear or branched.

[0577] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[0578] The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

[0579] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0580] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[0581] The above-mentioned aralkyl group means an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the above-mentioned alkyl groups and aryl groups.

[0582] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0583] These groups may further have a known substituent.

[0584] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0585] As the group that decomposes by the action of an acid to generate an alkali-soluble group or the group that leaves by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0586] Furthermore, as the compound having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl, a compound having at least one group selected from the group consisting of urea bond and urethane bond is also preferred. A preferred embodiment of the above compound is the same as the preferred embodiment of the crosslinking agent U except that the polymerizable group is at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl instead of a free radical polymerizable group.

[0587] As a compound having at least one group selected from acyloxymethyl, hydroxymethyl and hydroxyethyl, the following structures can be specifically cited. The compound having acyloxymethyl can be cited as a compound in which the alkoxymethyl of the following compound is changed to acyloxymethyl. As a compound having alkoxymethyl or acyloxymethyl in the molecule, the following compounds can be cited, but are not limited to these.

[0588] [Chemical formula 42]

[0589]

[0590] [Chemical formula 43]

[0591]

[0592] [Chemical formula 44]

[0593]

[0594] As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product may be used, or a compound synthesized by a known method may be used.

[0595] From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0596] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0597] Specific examples of the urea-based crosslinking agent include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, tetrabutoxymethylated glycoluril, and the like.

[0598] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0599] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[0600] Acrylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[0601] 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

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

[0603] As the compound having at least one group selected from a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0604] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzene hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Ketone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0605] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MX-100LM, NIKALAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0606] The resin composition of the present invention also preferably contains at least one compound selected from epoxy compounds, oxetane compounds and benzoxazine compounds as another crosslinking agent.

[0607] -Epoxy compounds (compounds having epoxy groups)-

[0608] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction below 200°C and does not cause a dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition can be effectively suppressed.

[0609] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

[0610] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specific examples include EPICLON (registered trademark, the same shall apply hereinafter) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON HP-4770, EPICLON EXA-830LVP, EPICLON EXA-8183, EPICLON EXA-8169, EPICLON N-660, EPICLON N-665-EXP-S, and EPICLON N-740 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark, the same shall apply hereinafter) BEO-20E, RIKARESIN BE0-60E, RIKARESIN HBE-100, RIKARESIN DME-100, and RIKARESIN L-200 (these are trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark, the same below) 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EPOLEAD (registered trademark, the same below) GT401, EPOLEAD PB4700, EPOLEAD PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (these are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.Also, the following compounds can be preferably used.

[0611] [Chemical formula 45]

[0612]

[0613] In the formula, n is an integer of 1-5, and m is an integer of 1-20.

[0614] In the above structure, from the viewpoint of achieving both improvement in heat resistance and elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[0615] -Oxetane compound (compound having an oxetane group)-

[0616] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As specific examples, ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0617] -Benzoxazine compound (compound having a benzoxazolyl group)-

[0618] The benzoxazine compound is preferred because it does not produce outgassing during curing due to the crosslinking reaction caused by the ring-opening addition reaction and further reduces thermal shrinkage to suppress the occurrence of warpage.

[0619] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine, (these are product names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0620] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. Other crosslinking agents may contain only one or more. When containing more than two other crosslinking agents, it is preferred that the total amount is within the above range.

[0621] 〔Polymerization initiator〕

[0622] The resin composition of the present invention contains a photopolymerization initiator.

[0623] The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, an activator that acts on a photoexcited sensitizer and generates active free radicals may also be used.

[0624] The photoradical polymerization initiator preferably contains at least one having a photopolymerization 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 absorption coefficient of a compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0625] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent 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, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, Japanese Patent Publication No. 6301489, 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 Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313 can be cited, and these contents are incorporated into this specification.

[0626] Examples of the ketone compound 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.

[0627] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

[0628] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0629] As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0630] As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. The contents are incorporated into the present specification.

[0631] As the photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator, so they are particularly preferred.

[0632] 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 Publication No. 2000-066385, the compounds described in Japanese Patent Publication No. 2004-534797, the compounds described in Japanese Patent Publication 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 Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc., are incorporated into the present specification.

[0633] Preferred oxime compounds include, for example, compounds of 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. The oxime compound as a photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0634] [Chemical formula 46]

[0635]

[0636] 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-301, TR-PBG-304, TR-PBG-305, and TR-PBG-3057 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), Quantacure PDO (manufactured by Wardblekinsop), and Omnirad 1316, Omnirad 1312 (manufactured by IGM Resins Co., Ltd.), SpeedCure PDO (manufactured by Sartomer Arkema). In addition, oxime compounds of the following structures can also be used.

[0637] [Chemical formula 47]

[0638]

[0639] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring, an oxime compound having a carbazole ring and having at least one benzene ring as a naphthalene ring skeleton, or an oxime compound having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can be used.

[0640] 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.

[0641] 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 OX1The electron withdrawing group may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acyl and nitro are preferred. Acyl is more preferred because it is easy to form a film with excellent light resistance, and benzoyl is further preferred. The benzoyl may have a substituent. As a substituent, a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclicoxy, alkenyl, alkylsulfanyl, arylsulfanyl, acyl or amino is preferred. An alkyl, alkoxy, aryl, aryloxy, heterocyclicoxy, alkylsulfanyl, arylsulfanyl or amino is more preferred. An alkoxy, alkylsulfanyl or amino is further preferred.

[0642] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2).

[0643] [Chemical formula 48]

[0644]

[0645] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfamoyl group,

[0646] 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,

[0647] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0648] However, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0649] In the above formula, preferably R X12 is an electron-withdrawing group, R X10 , R X11 , R X13 , R X14 A hydrogen atom.

[0650] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents are incorporated into the present specification.

[0651] Particularly preferred oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having thioaryl groups described in JP-A-2009-191061, and the like, and the contents thereof are incorporated into the present specification.

[0652] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably 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 their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0653] 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, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0654] 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 are incorporated into the present specification.

[0655] As the photo-radical polymerization initiator, a photo-radical polymerization initiator of difunctional or trifunctional or more can be used. By using this photo-radical polymerization initiator, more than two free radicals are produced from one molecule of the photo-radical polymerization initiator, so good sensitivity can be obtained. And, in the case of using a compound of asymmetric structure, crystallinity decreases and the solubility in solvents etc. improves, and becomes difficult to separate out over time, thus being able to improve the stability over time of resin combination. Specific examples of the bifunctional or trifunctional or higher-functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T 2010-527339, JP-T 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-T 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, compounds (E) described in JP-T 2013-522445, and compounds described in JP-T 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 Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[0656] 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 further preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one or more. When containing more than two photopolymerization initiators, the total amount is preferably within the above range.

[0657] In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, heating in an oven, a hot plate, or the like may further promote crosslinking by the photopolymerization initiator.

[0658] 〔Sensitizer〕

[0659] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., and generates electron transfer, energy transfer, heat generation, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases.

[0660] 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 azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0661] 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, and p-dimethylamino benzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)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 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, isopentyl dimethylaminobenzoate, diethylamino isopentyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0662] Furthermore, other sensitizing pigments may also be used.

[0663] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0664] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and further preferably 0.5 to 10 mass % relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0665] 〔Chain transfer agent〕

[0666] 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) pages 683-684. As chain transfer agents, for example, polyols having -SS-, -SO- 2 -S-, -NO-, SH, PH, SiH and GeH compound groups, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having thiocarbonylthio group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, etc. These can generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0667] 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 the present specification.

[0668] When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one or more. When there are two or more chain transfer agents, it is preferred that the total is within the above range.

[0669] <Alkali Generator>

[0670] The resin composition of the present invention may contain a base generator. Here, the base generator refers to a compound that can generate a base by physical action or chemical action. Preferred base generators include thermal base generators and photobase generators.

[0671] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferred that the resin composition contains an alkali generator. When the resin composition contains a thermal alkali generator, for example, the cyclization reaction of the precursor can be promoted by heating, thereby obtaining a cured product having good mechanical properties or chemical resistance, and, for example, having good performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package.

[0672] 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.

[0673] The base generating agent is not particularly limited, and a known base generating agent can be used. Examples of the known base generating agent include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imide salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimide compounds, and the like.

[0674] Specific examples of the nonionic base generating agent include compounds represented by formula (B1), formula (B2) or formula (B3).

[0675] [Chemical formula 49]

[0676]

[0677] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 Each independently represents an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 Not all of them have carboxyl groups. In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to the carbon atom of a hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed with the nitrogen atom, it is not a tertiary amine structure.

[0678] In formula (B1) and (B2), Rb 1 , Rb 2 and Rb 3Preferably at least one of the rings contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

[0679] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Preferably, it is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably a cyclohexyl group which may have a substituent.

[0680] As Rb 3 Examples of the group include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and more preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms), aralkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and more preferably 8 to 16 carbon atoms), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 12 carbon atoms), and aralkyloxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms). Among these, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferred. R 3 It may further have a substituent.

[0681] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0682] [Chemical formula 50]

[0683]

[0684] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 The meanings are the same as Rb in formula (B1) 1 and Rb 2 have the same meaning.

[0685] R 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent. 13 Aralkyl groups are preferred.

[0686] R 33 and Rb 34 Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0687] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and an aryl group is preferred.

[0688] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0689] [Chemical formula 51]

[0690]

[0691] R 11 and Rb 12The meaning is the same as Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0692] R 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0693] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0694] [Chemical formula 52]

[0695]

[0696] In formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 or more. N1 and R N2 Each independently represents a monovalent organic group.

[0697] In this specification, "connection chain" refers to the shortest (smallest number of atoms) chain connecting two atoms or connecting atom groups of connection objects in the atomic chain on the path connecting these connection objects. For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the connection chain is composed of four carbon atoms, and the number of atoms on the path of the connection chain (that is, the number of atoms constituting the connection chain, hereinafter also referred to as "connection chain length" or "length of the connection chain") is 4.

[0698] [Chemical formula 53]

[0699]

[0700] The number of carbon atoms in L of formula (B3) (including carbon atoms other than carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and most preferably 4. As specific preferred compounds of the alkali generator, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002 can also be cited.

[0701] Furthermore, the base generating agent also preferably contains a compound represented by the following formula (N1).

[0702] [Chemical formula 54]

[0703]

[0704] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0705] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and further preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that becomes the shortest distance between the two carbonyl groups in the formula.

[0706] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10), and specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10) can be mentioned, and an aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R N1 and R N2, the basicity of the generated base is high, so it is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, the aliphatic hydrocarbon group can be exemplified as having an oxygen atom in the hydrocarbon chain.

[0707] As a component of R N1 and R N2 Examples of the aliphatic hydrocarbon group include linear or branched chain alkyl groups, cyclic alkyl groups, groups containing a combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The number of carbon atoms in the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like.

[0708] The number of carbon atoms in the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0709] The number of carbon atoms of the group comprising a combination of a chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group comprising a combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0710] The number of carbon atoms in the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like, cyclic, linear or branched.

[0711] However, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 An alkyl group having 5 to 12 carbon atoms is preferred. However, in a formulation where adhesion to a metal (eg, copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0712] R N1 and R N2 The ring structure may have oxygen atoms in the chain. N1 and R N2The formed cyclic structure can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the formed cyclic structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring and a morpholine ring can be cited, and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring can be cited.

[0713] R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0714] As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid is preferably used.

[0715] As a specific example of the protecting group, a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain can be cited. As chain or cyclic alkyl groups, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. As chain alkyl groups having an oxygen atom in the chain, alkoxyalkyl groups can be cited, preferably methoxymethyl (MOM) groups, ethoxyethyl (EE) groups, etc. can be cited. As cyclic alkyl groups having an oxygen atom in the chain, epoxy groups, glycidyl groups, oxetanyl groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc. can be cited.

[0716] In formula (N1), the divalent linking group constituting L is not particularly limited, preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.

[0717] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and further preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. The number of carbon atoms in the group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., aralkylene group) is preferably 7 to 22, more preferably 7 to 18, and further preferably 7 to 10.

[0718] Specifically, the linking group L is preferably a linear or branched alkylene group, a cyclic alkylene group, a group containing a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

[0719] The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0720] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

[0721] The number of carbon atoms of the group consisting of a combination of a linear alkylene group and a cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0722] The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be linear or branched. The number of carbon atoms in the alkylene group having an oxygen atom in its chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0723] The number of carbon atoms in the linear or branched alkenylene group is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 3. The number of C═C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 3.

[0724] The number of carbon atoms in the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of C═C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0725] The arylene group has preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms.

[0726] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms.

[0727] Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, arylene groups, and alkylene groups; more preferred are 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and ethyleneoxyethylene (especially 1,2-ethyleneoxy-1,2-ethylene).

[0728] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0729] [Chemical formula 55]

[0730]

[0731] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0732] Specific examples of preferred compounds of the ionic base generator include compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0733] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0734] [Chemical formula 56]

[0735]

[0736] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0737] [Chemical formula 57]

[0738]

[0739] Furthermore, as the base generator, an amine in which the amino group is not protected by a tert-butoxycarbonyl group is preferred from the viewpoints of storage stability and deprotection during curing to generate a base.

[0740] 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-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl] Benzyl alcohol, diethanolamine, diisopropanolamine, 3-hydroxypyrrolidine, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidine)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetrahydrotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or an amino acid and a compound in which the amino group of the derivative is protected by a tert-butoxycarbonyl group, but the present invention is not limited thereto.

[0741] When the resin composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0742] The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

[0743] <Solvent>

[0744] The resin composition of the present invention preferably contains a solvent.

[0745] 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.

[0746] 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, methyl 3-ethoxypropionate, etc.) Preferred esters include 2-alkoxy alkyl propionates (e.g., 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, 2-alkoxy propyl propionate, etc. (e.g., 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate), 2-alkoxy-2-methyl methyl propionate and 2-alkoxy-2-methyl ethyl propionate (e.g., 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0747] Preferred 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.

[0748] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, 4-methylcyclohexanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0749] Examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred cyclic hydrocarbons include these.

[0750] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred sulfoxide.

[0751] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 2-hydroxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferred amides.

[0752] As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

[0753] Examples of the alcohol 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.

[0754] Regarding the solvent, a mixture of two or more solvents is also preferred from the viewpoint of improving the properties of the coating surface.

[0755] In the present invention, preferably, it is a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levulose ketone and dihydrolevulose ketone, or a mixed solvent consisting of two or more thereof. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N, N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate simultaneously. It is also one of the preferred embodiments of the present invention to further add about 1 to 10% by mass of toluene to the total mass of the solvent to the solvents used in combination.

[0756] Especially, from the viewpoint of the storage stability of resin combination etc., the mode that comprises gamma-valerolactone as solvent is also one of preferred modes of the present invention.In this mode, the content of gamma-valerolactone relative to the gross mass of solvent is preferably more than 50 mass %, more preferably more than 60 mass %, further preferably more than 70 mass %.And, the upper limit of above-mentioned content is not particularly limited, can be 100 mass %.Above-mentioned content considers the solubility of the composition such as the specific resin included in resin combination etc. to determine.

[0757] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide relative to the total mass of the solvent.

[0758] Furthermore, from the viewpoint of suppressing coating defects, the resin composition preferably contains a solvent having a ketone structure.

[0759] As the solvent containing a ketone structure, the solvents described as the above-mentioned ketones can be preferably cited. Among them, cyclic ketone compounds are particularly preferred. Cyclic ketone compounds refer to compounds having a cyclic structure and a ketone structure and containing a carbon atom contained in the ketone structure as a ring member of the cyclic structure.

[0760] The resin composition may contain only a ketone structure-containing solvent as a solvent, or may use a ketone structure-containing solvent and other solvents in mixture.

[0761] As the above-mentioned other solvents, the above-mentioned amides, esters, ureas or amides are preferred, and N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, or 2-hydroxy-N,N-dimethylpropionamide is more preferred.

[0762] When the resin composition contains a ketone structure-containing solvent and other solvents, the content of the ketone structure-containing solvent relative to the total content of the solvent is preferably 50 to 95% by mass, more preferably 60 to 90% by mass.

[0763] When the resin composition contains a ketone structure-containing solvent, it may contain only one ketone structure-containing solvent or two or more. When the resin composition contains two or more ketone structure-containing solvents and other solvents, the total amount of the ketone structure-containing solvents is preferably within the above range.

[0764] From the viewpoint of coating property, the content of the solvent is preferably set to a total solid content concentration of the resin composition of the present invention of 5 to 80% by mass, more preferably set to a total solid content of 5 to 75% by mass, further preferably set to a total solid content of 10 to 70% by mass, and further preferably set to a total solid content of 20 to 70% by mass. The solvent content can be adjusted according to the thickness and coating method required for the coating film. When containing two or more solvents, it is preferred that the total is within the above range.

[0765] <Metal Adhesion Improver>

[0766] From the viewpoint of improving the adhesion to the metal material used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion improver. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0767] 〔Silane coupling agent〕

[0768] As a silane coupling agent, 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 Publication No. 2018-173573 can be cited, and these contents are incorporated into this specification. For example, as commercially available products, KBM-403, KBM-573, KBE-903, X-12-989MS, X-12-1214A, X-12-1281C, X-12-1288 (the above are made by Shin-Etsu Chemical Co., Ltd.) and the like can be cited. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. The following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R may include a structure of a blocking agent derived from a blocked isocyanate group. As a blocking agent, it can be selected according to the detachment temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be mentioned. For example, from the viewpoint of setting the detachment temperature to 160 to 180° C., caprolactam, etc. are preferred. As a commercial product of such a compound, X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

[0769] [Chemical formula 58]

[0770]

[0771] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Acyloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilyl propyl succinic anhydride. These can be used alone or in combination of two or more.

[0772] Furthermore, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can also be used.

[0773] Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0774] [Chemical formula 59]

[0775]

[0776] 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.

[0777] R S1It is preferred to have a structure containing 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 cited. As a group with an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group with an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (methyl) acrylamide group, a (methyl) acryloxy group, etc. can be cited, preferably vinylphenyl, (methyl) acrylamide group or (methyl) acryloxy group, more preferably vinylphenyl or (methyl) acryloxy group, further preferably (methyl) acryloxy group.

[0778] R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

[0779] n represents an integer of 0 to 2, and 1 is preferred.

[0780] 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.

[0781] 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.

[0782] 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.).

[0783] 〔Aluminum-based adhesive additive〕

[0784] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0785] 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 the present specification.

[0786] 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 further 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 more. When using more than two, it is preferred that the total is within the above range.

[0787] <Migration Inhibitor>

[0788] The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0789] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, and a triazine ring), compounds having a thiourea or sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and 5-methylbenzotriazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0790] As the migration inhibitor, an ion capture agent that captures anions such as halogen ions may also be used.

[0791] 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, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and these contents are incorporated into this specification.

[0792] Specific examples of the migration inhibitor include the following compounds.

[0793] [Chemical formula 60]

[0794]

[0795] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0796] The migration inhibitor may be one or two or more. When the migration inhibitor is two or more, the total amount thereof is preferably within the above range.

[0797] <Light absorber>

[0798] From the viewpoint of resolution, the resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at an exposure wavelength decreases upon exposure.

[0799] Whether a certain compound a contained in the resin composition corresponds to the light absorber (that is, whether the absorbance at the exposure wavelength decreases due to exposure) can be determined by the following method.

[0800] First, a solution of compound a having the same concentration as that contained in the resin composition is prepared, and the molar absorption coefficient (mol -1 ·L·cm -1 , also referred to as "molar absorption coefficient 1". ). In order to reduce the influence of changes such as the decrease in the molar absorption coefficient of compound a, the above measurement is performed quickly. Regarding the solvent in the above solution, the solvent is used when the resin composition contains a solvent, and N-methyl-2-pyrrolidone is used when the resin composition does not contain a solvent.

[0801] Next, the solution of the compound a was irradiated with exposure light. The cumulative amount of exposure light was 800 mJ for 1 mol of the compound a.

[0802] Then, the molar absorption coefficient (mol -1 ·L·cm -1 , also known as the "molar absorption coefficient 2". ).

[0803] The attenuation rate (%) is calculated from the above-mentioned molar absorption coefficient 1 and molar absorption coefficient 2 according to the following formula. When the attenuation rate (%) is 5% or more, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases upon exposure (i.e., a light absorber).

[0804] Attenuation rate (%) = 1-molar absorption coefficient 2 / molar absorption coefficient 1×100

[0805] The attenuation rate is preferably 10% or more, and more preferably 20% or more. The lower limit of the attenuation rate is not particularly limited, and may be 0% or more.

[0806] The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form a photosensitive film.

[0807] The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity. The photopolymerization initiator having sensitivity to a certain wavelength means that polymerization initiating species are generated when the photopolymerization initiator is exposed to light at a certain wavelength.

[0808] As for the wavelength of the above-mentioned exposure light, in relation to the light source, there are (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc.

[0809] The wavelength of the exposure light may be any wavelength to which the photopolymerization initiator is sensitive, and h-rays (wavelength: 405 nm) or i-rays (wavelength: 365 nm) are preferred, and i-rays (wavelength: 365 nm) are more preferred.

[0810] The light absorber may be a compound that generates a radical polymerization initiating species upon exposure, but is preferably a compound that does not generate a radical polymerization initiating species upon exposure from the viewpoint of resolution and chemical resistance.

[0811] Whether or not the light absorber is a compound that generates a radical polymerization initiating species upon exposure can be determined by the following method.

[0812] A solution containing a light absorber and a radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, as the radical crosslinking agent in the above solution, a compound identical to that contained in the resin composition is used at the same concentration. When the resin composition does not contain a radical crosslinking agent, methyl methacrylate is used at a concentration 5 times that of the light absorber.

[0813] Thereafter, exposure light was irradiated, and the accumulated exposure amount was set to 500 mJ.

[0814] After exposure, polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography. When the ratio of the molar amount of the polymerizable compound polymerized to the total molar amount of the polymerizable compound is 10% or less, the light absorber is determined to be a compound that does not generate a radical polymerization initiating species by exposure.

[0815] The above molar ratio is preferably 5% or less, and more preferably 3% or less. The lower limit of the above molar ratio is not particularly limited, and may be 0%.

[0816] The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form a photosensitive film.

[0817] The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

[0818] As the compound that generates free radical polymerization initiating species upon exposure, the same compounds as the above-mentioned photo radical polymerization initiator can be cited. When the composition contains a photo radical polymerization initiator as a light absorber, the compound with the lowest polymerization initiating ability of the generated free radical species is used as the light absorber, and the rest is used as the photopolymerization initiator.

[0819] Examples of the compound that does not generate a radical polymerization initiating species by exposure include, in addition to a photoacid generator and a photobase generator, a pigment whose absorption wavelength changes by exposure.

[0820] Among them, the light absorber is preferably naphthoquinone diazide or a dye whose absorbance changes upon exposure, and more preferably naphthoquinone diazide.

[0821] Furthermore, as the light absorber, for example, it is also conceivable to use a photoacid generator or a photobase generator in combination with a compound whose absorbance at the exposure wavelength decreases depending on pH.

[0822] 〔Naphthoquinone diazide〕

[0823] Examples of the naphthoquinonediazide include compounds that generate indenecarboxylic acid upon exposure and whose absorbance at the exposure wavelength decreases, and compounds having a 1,2-naphthoquinonediazide structure are preferred.

[0824] As the naphthoquinone diazide compound, naphthoquinone diazide sulfonic acid ester of a hydroxy compound is preferred.

[0825] As the hydroxy compound, a compound represented by any one of the following formulas (H1) to (H6) is preferred.

[0826] [Chemical formula 61]

[0827]

[0828] In formula (H1), R 1 and R 2 Each independently represents a monovalent organic group, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group; n1, n2, m1 and m2 each independently represent an integer of 0 to 5; and at least one of m1 and m2 represents an integer of 1 to 5.

[0829] In formula (H2), Z represents a tetravalent organic group, L 1 , L 2 , L 3 and L 4 Each independently represents a single bond or a divalent organic group, R 5 , R 6 , R 7 and R 8 Each independently represents a monovalent organic group, n3, n4, n5 and n6 each independently represent an integer of 0 to 3, m3, m4, m5 and m6 each independently represent an integer of 0 to 2, and at least one of m3, m4, m5 and m6 is 1 or 2.

[0830] In formula (H3), R 9 and R 10 Each independently represents a hydrogen atom or a monovalent organic group, L 5 Each independently represents a divalent organic group, and n7 represents an integer of 3-8.

[0831] In formula (H4), L 6 Represents a divalent organic group, L 7 and L 8 Each independently represents a divalent organic group containing an aliphatic tertiary carbon atom or a quaternary carbon atom.

[0832] In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, L 9 , L 10 and L 11 Each independently represents a single bond or a divalent organic group; m7, m8, m9, and m10 each independently represents an integer of 0 to 2; and at least one of m7, m8, m9, and m10 is 1 or 2.

[0833] In formula (H6), R 42 , R 43 , R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, R 46 and R 47 Each independently represents a monovalent organic group, n16 and n17 each independently represent an integer of 0 to 4, m11 and m12 each independently represent an integer of 0 to 4, and at least one of m11 and m12 is an integer of 1 to 4.

[0834] In formula (H1), R 1 and R 2 Each of R is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 1 and R 2 The monovalent organic group in the amine group may be a hydrocarbon group which may have a substituent, for example, an aromatic hydrocarbon group which may have a substituent such as a hydroxyl group, etc.

[0835] In formula (H1), R 3 and R 4 Each of R is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 3 and R 4 The monovalent organic group in the amine group may be a hydrocarbon group which may have a substituent, for example, a hydrocarbon group which may have a substituent such as a hydroxyl group, etc.

[0836] In formula (H1), n1 and n2 are each independently preferably 0 or 1, and more preferably 0.

[0837] In formula (H1), both m1 and m2 are preferably 1.

[0838] The compound represented by formula (H1) is preferably a compound represented by any one of formula (H1-1) to formula (H1-5).

[0839] [Chemical formula 62]

[0840]

[0841] In formula (H1-1), R 21 , R 22 and R 23 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a group represented by the following formula (R-1).

[0842] [Chemical formula 63]

[0843]

[0844] In formula (R-1), R 29 represents a hydrogen atom, an alkyl group or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding position to other structures.

[0845] In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0846] In formula (H1-2), R 24 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15, and n16 each independently represent an integer of 0 to 2. 30 represents a hydrogen atom or an alkyl group.

[0847] In formula (H1-3), R 25 , R 26 , R 27 and R 28 Each independently represents a monovalent organic group, and is preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1).

[0848] In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0849] As the compound represented by the formula (H1-1), a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4) is preferred.

[0850] As the compound represented by the formula (H1-2), a compound represented by the following formula (H1-2-1) or (H1-2-2) is preferred.

[0851] As the compound represented by the formula (H1-3), compounds represented by the following formulas (H1-3-1) to (H1-3-3) are preferred.

[0852] [Chemical formula 64]

[0853]

[0854] In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulae (Z-1) to (Z-4). In the following formulae (Z-1) to (Z-4), * represents a bonding position to another structure.

[0855] [Chemical formula 65]

[0856]

[0857] In formula (H2), L 1 , L 2 , L 3 and L 4 Each independently is preferably a single bond or a methylene group.

[0858] In formula (H2), R 5 , R 6 , R 7 and R 8 Each independently is preferably an organic group having 1 to 30 carbon atoms.

[0859] In formula (H2), n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0860] In formula (H2), m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1.

[0861] Examples of the compound represented by formula (H2) include compounds having the following structures.

[0862] [Chemical formula 66]

[0863]

[0864] In formula (H3), R 9 and R 10 Each independently preferably represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0865] In formula (H3), L 5 Each independently is preferably a group represented by the following formula (L-1).

[0866] [Chemical formula 67]

[0867]

[0868] In formula (L-1), R 30 represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding position to another structure.

[0869] In formula (H3), n7 is preferably an integer of 4-6.

[0870] Examples of the compound represented by formula (H3) include the following compounds. In the following formula, n each independently represents an integer of 0 to 9.

[0871] [Chemical formula 68]

[0872]

[0873] In formula (H4), L 6 Preferably -C(CF 3 ) 2 -、-S(=O) 2 -or -C(=O)-.

[0874] In formula (H4), L 7 and L 8 Each independently is preferably a divalent organic group having 2 to 20 carbon atoms.

[0875] Examples of the compound represented by formula (H4) include the following compounds.

[0876] [Chemical formula 69]

[0877]

[0878] In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 A hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group is respectively independently preferred.

[0879] In formula (H5), L 9 , L 10 and L 11 Preferably, each independently is a single bond, -O-, -S-, -S(=O) 2 -, -C(=O)-, -C(=O)O-, cyclopentylene, cyclohexylene, phenylene or a divalent organic group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulas (L-2) to (L-4).

[0880] [Chemical formula 70]

[0881]

[0882] In formula (L-2) to formula (L-4), R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R 34 , R 35 , R 36 and R 37 Each independently represents a hydrogen atom or an alkyl group, n15 is an integer from 1 to 5, and R 38 , R 39 , R40 and R 41 Each independently represents a hydrogen atom or an alkyl group, and * represents a bonding position to other structures.

[0883] Examples of the compound represented by formula (H5) include the following compounds.

[0884] [Chemical formula 71]

[0885]

[0886] In formula (H6), R 42 , R 43 , R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

[0887] In formula (H6), R 46 and R 47 An alkyl group, an alkoxy group or an aryl group is respectively and independently preferred, and an alkyl group is more preferred.

[0888] In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0889] In formula (H6), n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3.

[0890] Examples of the compound represented by formula (H6) include the following compounds.

[0891] [Chemical formula 72]

[0892]

[0893] Examples of the hydroxy compounds include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4,6,3′,4′-pentahydroxybenzophenone, 2,3,4,2′,4′-pentahydroxybenzophenone, 2,3,4,2′,5′-pentahydroxybenzophenone, 2,4,6,3′,4′,5′-hexahydroxybenzophenone, and 2,3,4,3′,4′,5′-hexahydroxybenzophenone;

[0894] Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyvalerophenone, 2,3,4-trihydroxyhexanophenone,

[0895] Bis((poly)hydroxyphenyl)alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl)propane-1, nordihydroguaiaretic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane,

[0896] Polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate,

[0897] Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)-methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-trihydroxybenzoyl)benzene and other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls,

[0898] Alkylene-bis(polyhydroxybenzoates) such as ethylene glycol-bis(3,5-dihydroxybenzoate) and ethylene glycol-bis(3,4,5-trihydroxybenzoate),

[0899] 2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3′,5′-biphenyltetraol, 2,4,2′,4′-biphenyltetraol, 2,4,6,3′,5′-biphenylpentaol, 2,4,6,2′,4′,6′-biphenylhexanol, 2,3,4,2′,3′,4′-biphenylhexanol and other polyhydroxy biphenyls,

[0900] 4,4'-thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides,

[0901] 2,2',4,4'-Tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers,

[0902] 2,2',4,4'-tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl) sulfoxides,

[0903] 2,2',4,4'-diphenyl sulfone and other bis(polyhydroxyphenyl) sulfones,

[0904] tris(4-hydroxyphenyl)methane, 4,4′,4″-trihydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4′-(3,4-diol-benzylidene)bis[2,6-dimethylphenol, 4,4′-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4′,2″,3″,4″-pentahydroxy-3,5,3′ , 5'-tetramethyltriphenylmethane, 2,3,4,2',3',4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2',3',4',3",4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane and other polyhydroxytriphenylmethanes, 4,4'-(phenylmethylene)bisphenol, 4,4'-(1-phenyl-ethylidene)bis[2-methylphenol], 4,4',4"-ethylidene-triphenol and other polyhydroxytriphenylethanes,

[0905] 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-5,6,5',6'-tetraol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indane-5,6,7,5',6',7'-hexaol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indane polyhydroxy spirobis-indanes such as 4,5,6,4',5',6'-hexanol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indanes-4,5,6,5',6',7'-hexanol, polyhydroxy spirobis-indanes such as 2,4,4-trimethyl-2',4',7'-trihydroxyflavanes,

[0906] Polyhydroxyphthalides such as 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3',4',5',6'-tetrahydroxybis[phthalide-3,9'-xanthen], flavonoid pigments such as morin, quercetin, and rutin,

[0907] α,α',α"-tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3-methyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene phenyl) 1,3,5-triisopropylbenzene, α,α',α"-tri(3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α',α"-tri(2,4-dihydroxyphenyl) 1,3,5-triisopropylbenzene, 1,3,5-tri(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tri(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tri(3,5-dimethyl-4-hydroxyphenylthiomethyl)-mesitylene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-3-[α,α'-bis(4"-hydroxyphenyl)ethyl]benzene bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(3'',5''-dimethyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3''-methyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3''-methoxy-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4-[α ',α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α',α'-bis(4''-hydroxyphenyl)ethyl]benzene and the like polyhydroxy compounds described in Japanese Patent Laid-Open No. 4-253058, α,α,α',α',α'',α''-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene and the like polyhydroxy compounds described in Japanese Patent Laid-Open No. 5-224410, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane and the like poly(hydroxyphenyl)alkanes described in Japanese Patent Laid-Open No. 5-303200 and EP-530148,

[0908] p-Bis(2,3,4-trihydroxybenzoyl)benzene, p-Bis(2,4,6-trihydroxybenzoyl)benzene, m-Bis(2,3,4-trihydroxybenzoyl)benzene, m-Bis(2,4,6-trihydroxybenzoyl)benzene, p-Bis(2,5-dihydroxy-3-bromobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-nitrobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5 -cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-tetrakis(2,3,4-trihydroxybenzoyl)benzene, α,α'-bis(2,3,4-trihydroxybenzoyl)p-xylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl)mesitylene,

[0909] 2,6-bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis-(2-hydroxy-5′-methylbenzyl)-p-cresol, 2,6-bis-(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-bis-(4-hydroxy-3,5-dimethylbenzyl)-pyrogallol, 2,6-bis-( 4-hydroxy-3,5-dimethylbenzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethyl-phenol, 4,6-bis-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-phenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol, 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy -3,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2',6,6'-tetrakis[(4-hydroxyphenyl)methyl]-4,4'-methylenediphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, 2,2',6,6'-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, [(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4'-methylenediphenol, 2,2'-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]6,6'-dimethyl-4,4'-methylenediphenol, 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobis(1H-indene)-5,5',6,6',7,7'hexanol, bis(4-hydroxy-3,5-dimethylphenyl)methyl)-(4-hydroxy-3-methoxyphenyl)methane, and the like.

[0910] Furthermore, low-nuclear forms of phenolic resins such as novolac resins can also be used.

[0911] Examples of the naphthoquinonediazidesulfonic acid include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and these may be used in combination.

[0912] The method for producing the naphthoquinonediazidesulfonic acid ester of a hydroxy compound is not particularly limited, but it can be obtained, for example, by sulfonylation of naphthoquinonediazidesulfonic acid with chlorosulfonic acid or thionyl chloride and condensation reaction of the obtained naphthoquinonediazidesulfonyl chloride with a hydroxy compound.

[0913] For example, it can be obtained by reacting a hydroxy compound with a predetermined amount of naphthoquinonediazidesulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and washing and drying the obtained product.

[0914] The esterification rate of naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, and more preferably 20% or more. The upper limit of the esterification rate is not particularly limited, and may be 100%.

[0915] The above esterification rate can be expressed as the ratio of esterified groups in the hydroxyl groups of the hydroxyl compound. 1 Confirmed by H-NMR etc.

[0916] Furthermore, as the light absorber, the compounds described in paragraphs 0088 to 0108 of JP-A-2019-206689 can also be used.

[0917] 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% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0918] In particular, from the viewpoint of improving adhesion to the substrate, the resin composition of the present invention preferably further contains the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, it is easy to maintain adhesion to the substrate even after the cured product is exposed under high temperature and high humidity conditions.

[0919] <Polymerization Inhibitor>

[0920] 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.

[0921] Specific examples of the polymerization inhibitor 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, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents are incorporated into this specification.

[0922] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass based on the total solid content of the resin composition.

[0923] The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0924] <Other additives>

[0925] Resin composition of the present invention can contain various additives as required within the scope of the effect of the present invention, for example, surfactant, higher fatty acid derivative, thermal polymerization initiator, inorganic particles, ultraviolet absorber, organic titanium compound, antioxidant, light acid generator, anti-agglomeration agent, phenolic compound, other polymer compounds, plasticizer and other auxiliary agents (for example, defoamer, flame retardant, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. About these components, for example, the records of 0183 sections after (0237 sections of corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification) of Japanese Patent Application Publication No. 2008-250074, 0101~0104, 0107~0109 sections, etc. can be referred to in the present specification, and these contents are incorporated in this specification. When these additives are matched, it is preferred that the total content is set to less than 3% by mass of the solid content of the resin composition of the present invention.

[0926] 〔Surfactant〕

[0927] The resin composition preferably contains a surfactant from the viewpoint of exhibiting leveling properties during drying, suppressing coating film defects, and improving flatness.

[0928] As the surfactant, various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0929] Among them, compounds containing a silicon atom are preferred, and silicone-based surfactants are more preferred.

[0930] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when preparing the coating liquid composition can be further improved, and the uniformity of the coating thickness or the liquid saving can be further improved. That is, when a coating liquid containing a surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating property of the coated surface. Therefore, it is more preferable to form a uniform film with less uneven thickness.

[0931] Examples of the fluorine-based surfactant include compounds described in paragraph 0328 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0932] As the fluorine-based surfactant, a fluorine-containing polymer compound can be preferably used, which contains: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups), for example, the following compounds can be mentioned.

[0933] [Chemical formula 73]

[0934]

[0935] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0936] Regarding fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups in the side chains can also be used as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited, and the contents are incorporated into this specification. In addition, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC CORPORATION can be cited.

[0937] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the perspective of uniformity of the thickness of the coating film or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

[0938] Examples of the silicone-based surfactant, hydrocarbon-based surfactant, nonionic surfactant, cationic surfactant, and anionic surfactant include compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0939] The surfactant may be used alone or in combination of two or more.

[0940] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0941] 〔Higher fatty acid derivatives〕

[0942] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention so as to be unevenly present on the surface of the resin composition of the present invention during the drying process after coating.

[0943] Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0944] When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition. The higher fatty acid derivative may be only one or more than two. When the higher fatty acid derivative is more than two, the total is preferably within the above range.

[0945] 〔Thermal polymerization initiator〕

[0946] As a thermal polymerization initiator, for example, a thermal free radical polymerization initiator can be cited. A thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, thereby further reducing the curing temperature or improving solvent resistance. In addition, a photopolymerization initiator sometimes has the function of initiating polymerization by heat, and thus can sometimes be added as a thermal polymerization initiator.

[0947] 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.

[0948] 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 further preferably 0.5 to 15% by mass relative to the total solid content of the resin composition. The thermal polymerization initiator may contain only one or more than two. When containing more than two thermal polymerization initiators, the total amount is preferably within the above range.

[0949] 〔Inorganic particles〕

[0950] Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0951] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0952] The average particle size of the inorganic particles is a secondary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.), for example.

[0953] When the above measurement is difficult to perform, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.

[0954] 〔Ultraviolet light absorber〕

[0955] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.

[0956] Specific examples of the ultraviolet absorber include compounds described in 0341 to 0342 of International Publication No. 2021 / 112189, and the contents are incorporated into the present specification.

[0957] The ultraviolet absorber may be used alone or in combination of two or more.

[0958] When the resin composition contains a UV absorber, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, based on the total solid content of the resin composition.

[0959] 〔Organotitanium compounds〕

[0960] Since the resin composition contains the organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[0961] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0962] Specific examples of the organic titanium compound are shown in the following I) to VII).

[0963] I) Titanium chelate compound: From the viewpoint that the storage stability of the resin composition is excellent and a good curing pattern can be obtained, a titanium chelate compound having more than two alkoxy groups is more preferably used. Specific examples are diisopropyl bis(triethanolamine) titanium, di(n-butyl alcohol)bis(2,4-pentanedione) titanium, diisopropyl bis(2,4-pentanedione) titanium, diisopropyl bis(tetramethylheptanedione) titanium, diisopropyl bis(ethyl acetoacetate) titanium, etc.

[0964] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[0965] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0966] IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylbenzene sulfonate)titanium isopropoxide, and the like.

[0967] V) Titanium oxide compound: for example, bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, titanium phthalocyanine oxide, and the like.

[0968] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0969] VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate.

[0970] Among them, as the organic titanium compound, from the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) titanocene compounds is preferred. In particular, bis(ethyl acetoacetate)titanium diisopropoxide, tetra(n-butoxide)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0971] Furthermore, it is also preferred that a compound represented by the following formula (T-1) is contained as the organic titanium compound or in place of the organic titanium compound.

[0972] [Chemical formula 74]

[0973]

[0974] In formula (T-1), M is titanium, zirconium or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, 11+l2×2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, 11+12+m+n×2=4, R 11 are independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy or substituted or unsubstituted phenoxy, R 12 is a substituted or unsubstituted hydrocarbon group, R 2 Each independently represents a group having a structure represented by the following formula (T-2), R 3 Each independently represents a group having a structure represented by the following formula (T-2), X A are each independently an oxygen atom or a sulfur atom.

[0975] [Chemical formula 75]

[0976]

[0977] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, * represents a bonding position to other structures, and # represents a bonding position to a metal atom.

[0978] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium.

[0979] In formula (T-1), an embodiment in which 11 and 12 are 0 is also one of the preferred embodiments of the present invention.

[0980] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0981] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0982] Here, in formula (T-1), it is also preferred that 11 and 12 are 0, and m is 0, 2 or 4.

[0983] In formula (T-1), from the viewpoint of stability of the specific metal complex, R 11 Substituted or unsubstituted cyclopentadiene ligands are preferred.

[0984] And, R 11 The cyclopentadienyl group, alkoxy group and phenoxy group in the group may be substituted, but an unsubstituted embodiment is also one of the preferred embodiments of the present invention.

[0985] In formula (T-1), R 12 It is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.

[0986] As R 12 The hydrocarbon group in may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and is preferably an aromatic hydrocarbon group.

[0987] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0988] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and further preferably a phenylene group.

[0989] As R 12 The substituent in is preferably a monovalent substituent, and examples thereof include a halogen atom. 12 In the case of an aromatic hydrocarbon group, it may have an alkyl group as a substituent.

[0990] Among them, in formula (T-1), R 12 Preferably, it is an unsubstituted phenylene group. 12 The phenylene group in the is preferably 1,2-phenylene group.

[0991] In formula (T-1), m is 2 or more, and in the case of containing 2 or more R 2 In the case of two or more R 2 The structures of can be the same or different.

[0992] In formula (T-1), n ​​is 2 or more, and in the case of containing 2 or more R 3 In the case of two or more R 3 The structures of can be the same or different.

[0993] In formula (T-2), X 1 ~X 3 Each independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0994] Specific examples of the compound represented by formula (T-1) include compounds corresponding to I-5 to I-8 in Examples, but are not limited to these.

[0995] When an organic titanium compound is contained, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when the content is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0996] 〔Antioxidant〕

[0997] By containing an antioxidant as an additive, the elongation characteristics of the cured film or the adhesion to the metal material can be improved. As antioxidants, phenol compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As specific examples of antioxidants, compounds described in 0348 to 0357 of International Publication No. 2021 / 112189 can be mentioned, and the content is incorporated into this specification.

[0998] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving the elongation characteristics or the adhesion to the metal material, and by setting it to 10 parts by mass or less, for example, by interacting with the photosensitive agent to improve the sensitivity of the resin composition. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount of these is preferably within the above range.

[0999] 〔Anti-agglomerating agent〕

[1000] As the anti-agglomerating agent, sodium polyacrylate and the like can be mentioned.

[1001] The anti-agglomerating agent may be used alone or in combination of two or more.

[1002] When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, based on the total solid content mass of the resin composition.

[1003] 〔Phenolic compounds〕

[1004] As phenolic compounds, there can be mentioned Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAICORPORATION), etc.

[1005] The phenolic compounds may be used alone or in combination of two or more.

[1006] When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, based on the total solid content mass of the resin composition.

[1007] 〔Other polymer compounds〕

[1008] Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerization with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

[1009] The other polymer compounds may be used alone or in combination of two or more.

[1010] When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass % to 30 mass % and more preferably 0.02 mass % to 20 mass % based on the total solid content of the resin composition.

[1011] <Characteristics of Resin Composition>

[1012] 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 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. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000mm 2 / s or more, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000mm 2 / s or less, a coating film having an excellent coating surface shape can be obtained.

[1013] <Restrictions on substances contained in the resin composition>

[1014] The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and further 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.

[1015] 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.

[1016] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., except for metals contained as complexes of organic compounds and metals. When containing multiple metals, the total amount of these metals is preferably within the above range.

[1017] In addition, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be listed: selecting raw materials with a low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

[1018] Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the halogen atoms present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably within the above range, respectively.

[1019] As a method for adjusting the content of halogen atoms, ion exchange treatment or the like is preferably mentioned.

[1020] As a storage container for the resin composition of the present invention, a conventionally known storage container can be used. As a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multilayer bottle having an inner wall of the container composed of six kinds of six layers of resins or a bottle having a seven-layer structure formed of six kinds of resins is also preferably used. As such a container, for example, a container described in Japanese Patent Publication No. 2015-123351 can be cited.

[1021] <Cured product of resin composition>

[1022] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1023] The cured product of the present invention is a cured product obtained by curing the resin composition.

[1024] The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and a film, a rod, a sphere, a granular shape, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in a film shape. Through the pattern processing of the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5μm or more and 150μm or less.

[1025] The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula.

[1026] Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[1027] <Characteristics of Cured Product of Resin Composition>

[1028] The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, the cured product may have excellent mechanical properties.

[1029] 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.

[1030] 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.

[1031] Furthermore, the dielectric loss tangent of the cured product of the resin composition of the present invention at 28 GHz is preferably 0.01 or less. The dielectric loss tangent can be measured by the method described in the examples described below.

[1032] <Preparation of resin composition>

[1033] 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.

[1034] Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing while rotating a pot.

[1035] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[1036] For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to filter using a filter. Regarding the filter pore size, for example, it is preferably less than 5 μm, more preferably less than 1 μm, further preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter can use a filter pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting a HDPE filter with a pore size of 1 μm as the first section and a HDPE filter with a pore size of 0.2 μm as the second section in series can be cited. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be a circulation filtration. In addition, filtering can also be performed after pressurization. When filtering is performed after pressurization, the pressure applied is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, further preferably 0.05 MPa to 0.7 MPa, and still further preferably 0.05 MPa to 0.5 MPa.

[1037] In addition to filtering using a filter, an impurity removal treatment using an adsorbent may also be performed. Filter filtering and impurity removal treatment using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[1038] After filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[1039] (Method for producing cured product)

[1040] 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.

[1041] 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 developing step of developing the film exposed in the exposure step with a developer to form a pattern.

[1042] The method for producing a cured product particularly preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.

[1043] Furthermore, the method for producing a cured product preferably includes the film forming step and the step of heating the film.

[1044] Hereinafter, the details of each step will be described.

[1045] <Film Formation Step>

[1046] The resin composition of the present invention can be used in a film forming step of forming a film on a substrate.

[1047] 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.

[1048] 〔Base material〕

[1049] The type of substrate can be appropriately determined according to the purpose and is not particularly limited. As the substrate, there can be cited semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, non-silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates (for example, it can be any one of a substrate formed by a metal and a substrate having a metal layer formed by, for example, plating, vapor deposition, etc.), paper, SOG (Spin On Glass: Spin-on Glass), TFT (Thin Film Transistor) array substrate, mold substrate, plasma display panel (PDP) electrode plate, etc. In particular, the substrate is preferably a semiconductor manufacturing substrate, and more preferably a silicon substrate, a Cu substrate and a mold substrate.

[1050] On the surface of these substrates, a layer such as an adhesive layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided.

[1051] The shape of the substrate is not particularly limited, and may be circular or rectangular.

[1052] Regarding the size of the substrate, for example, if the substrate is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm, and for example, if the substrate is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.

[1053] As the substrate, for example, a plate-shaped substrate (substrate) can be used, and preferably a panel-shaped substrate (substrate) is used.

[1054] When a film is formed by applying the resin composition to the surface of a resin layer (for example, a layer composed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[1055] As a method of applying the resin composition to a substrate, coating is preferred.

[1056] As the method applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be cited. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating or inkjet are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. The solid content concentration or coating conditions of the resin composition are adjusted according to the method applied, thereby obtaining a film of the desired thickness. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating or spray coating, inkjet, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[1057] Furthermore, a method of transferring a coating film formed on a temporary support body in advance by the above-mentioned imparting method to a substrate can also be applied.

[1058] As for the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[1059] Furthermore, a process of removing excess film at the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backside rinse.

[1060] A pre-wetting step may be adopted in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[1061] <Drying process>

[1062] After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

[1063] That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.

[1064] The drying step is preferably performed after the film forming step and before the exposure step.

[1065] The film drying temperature in the drying step is preferably 50° C. to 150° C., more preferably 70° C. to 130° C., and further preferably 90° C. to 110° C. Furthermore, the drying may be performed by reducing pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[1066] <Exposure Process>

[1067] The film may be subjected to an exposure step of selectively exposing the film.

[1068] The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step.

[1069] Selective exposure refers to exposing a portion of the film to light, and by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.

[1070] The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured, but is preferably 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably 200 to 8,000 mJ / cm 2 .

[1071] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[1072] Regarding the exposure wavelength, in terms of its relationship with the light source, there are (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F 2 Excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. For the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-rays is more preferred from the viewpoint of exposure sensitivity.

[1073] The exposure method is not particularly limited as long as at least a portion of the film composed of the resin composition of the present invention is exposed. Examples of the exposure method include exposure using a photomask and exposure by laser direct imaging.

[1074] <Post-exposure heating process>

[1075] The film may be subjected to a step of heating after exposure (post-exposure heating step).

[1076] That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

[1077] The post-exposure heating step can be performed after the exposure step and before the development step.

[1078] The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[1079] The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1080] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature.

[1081] Furthermore, the heating rate can be appropriately changed during the heating process.

[1082] The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[1083] Furthermore, during heating, it is also preferred to conduct the heating in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[1084] <Development Process>

[1085] The film after exposure may be subjected to a developing step of developing with a developer to form a pattern.

[1086] That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step using a developing solution to form a pattern.

[1087] By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

[1088] Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[1089] 〔Developer〕

[1090] As a developer used in the development step, a developer containing an alkaline aqueous solution or an organic solvent can be mentioned.

[1091] When the developer is an alkali aqueous solution, examples of the alkaline compound that the alkali aqueous solution may contain include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, the developer is TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is used. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass, based on the total mass of the developer.

[1092] When the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. In addition, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be preferably listed, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be preferably listed.

[1093] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly preferred, a developer containing at least one selected from cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[1094] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[1095] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. When at least one of the alkaline compound and the alkali generator in the developer penetrates into the pattern, the performance of the pattern such as elongation at break may be improved.

[1096] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in a film after curing (adhesion to a substrate when the cured product is further heated).

[1097] As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides and the like are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred.

[1098] As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is not likely to remain in the cured film (the cured product obtained) is preferred, and from the viewpoint of promoting cyclization, a compound whose residual amount is not likely to be reduced by gasification before heating is preferred.

[1099] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101, 325 Pa).

[1100] The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[1101] For example, when the boiling point of the organic solvent is 100°C, the base used preferably has a boiling point of 80°C or higher, and more preferably has a boiling point of 100°C or higher.

[1102] The developer may contain only one kind of basic compound or two or more kinds thereof.

[1103] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butylenediamine, 1,5-diaminopentane, N-methylhexylamine , N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

[1104] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[1105] When the developer contains at least one of a basic compound and an alkali generator, the content of the basic compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1106] When the alkaline compound or the base generator is solid in an environment where the developer is used, the content of the alkaline compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the developer.

[1107] The developer may contain only one or more of the alkaline compound and the alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[1108] The developer may further contain other components.

[1109] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[1110] [Developer supply method]

[1111] As long as the desired pattern can be formed, the method of supplying the developer is not particularly limited, and there are the following methods: a method of immersing the substrate formed with a film in the developer, a method of supplying the developer to the film formed on the substrate using a nozzle by a capping immersion development, or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

[1112] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or continuously supply the developer using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply the developer using a spray nozzle.

[1113] In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[1114] Examples of a method for supplying the developer in the development step include a step of continuously supplying the developer to the substrate, a step of keeping the developer substantially stationary on the substrate, a step of vibrating the developer on the substrate using ultrasonic waves or the like, and a combination of these steps.

[1115] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[1116] In the development step, the pattern may be cleaned (rinsed) with a rinse liquid after the processing with the developer. Alternatively, a method may be adopted in which the rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[1117] 〔Rinsing fluid〕

[1118] When the developer is an alkaline aqueous solution, water can be used as the rinse liquid, and when the developer is a developer containing an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[1119] As the organic solvent in the case where the rinse solution contains an organic solvent, the same organic solvents as exemplified in the case where the developer contains an organic solvent can be mentioned.

[1120] The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility in the pattern than the organic solvent contained in the developer.

[1121] When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME, and further preferably cyclohexanone and PGMEA.

[1122] When the rinse liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to the total mass of the rinse liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinse liquid.

[1123] The rinse solution may contain at least one of a basic compound and an alkali generator.

[1124] Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, a basic compound, and an alkali generator is also one of the preferred embodiments of the present invention.

[1125] Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generator that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same.

[1126] The basic compound and the base generating agent contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.

[1127] When the rinse liquid contains at least one of a basic compound and an alkali generator, the content of the basic compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1128] When the basic compound or base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the rinse liquid.

[1129] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one alkaline compound and at least one of the alkali generators, or may contain at least one of two or more alkaline compounds and at least one of the alkali generators. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[1130] The rinsing solution may further contain other ingredients.

[1131] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[1132] [Method of supplying flushing fluid]

[1133] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinsing liquid, and the following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through liquid accumulation, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through a straight nozzle or the like.

[1134] From the viewpoint of the permeability of the rinse liquid, the removal of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., preferably a method of continuously supplying using a spray nozzle, and from the viewpoint of the permeability of the rinse liquid to the image part, more preferably a method of supplying using a spray nozzle. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[1135] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[1136] The method for supplying the rinsing liquid in the rinsing step may include continuously supplying the rinsing liquid to the substrate, maintaining the rinsing liquid in a substantially static state on the substrate, vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these.

[1137] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[1138] In the development process, after processing with a developer or cleaning the pattern with a rinse solution, a process of bringing the treatment solution into contact with the pattern may be included. In addition, a method of supplying the treatment solution before the developer or rinse solution in contact with the pattern is completely dried may also be adopted.

[1139] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator.

[1140] Preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator used in the rinse solution.

[1141] The method for supplying the processing liquid to the pattern can be the same method as the method for supplying the rinse liquid described above, and the preferred aspects are also the same.

[1142] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1143] Furthermore, when the basic compound or the base generating agent is solid in the environment where the treatment liquid is used, the content of the basic compound or the base generating agent is preferably 70 to 100% by mass relative to the total solid content of the treatment liquid.

[1144] When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one kind of at least one of the alkaline compound and the alkali generator, or may contain at least one of two or more kinds of the alkaline compound and the alkali generator. When at least one of the alkaline compound and the alkali generator is two or more kinds, it is preferred that the total amount thereof is within the above range.

[1145] <Heating process>

[1146] The pattern obtained by the development step (the pattern after the rinsing step when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development.

[1147] That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.

[1148] Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step or a film obtained by a film forming step.

[1149] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide.

[1150] Furthermore, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed.

[1151] The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, particularly preferably 160 to 230°C.

[1152] The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated by the base generating agent through heating.

[1153] The heating in the heating process is preferably performed at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The heating rate is more preferably 2 to 10°C / min, and further preferably 3 to 10°C / min. By setting the heating rate to be 1°C / min or more, productivity can be ensured and excessive volatilization of the acid or solvent can be prevented. By setting the heating rate to be 12°C / min or less, the residual stress of the cured product can be relaxed.

[1154] In the case of an oven capable of rapid heating, the temperature is increased from the temperature at the start of heating to the maximum heating temperature at a rate of preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and still more preferably 3 to 6°C / second.

[1155] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the dried film (layer), for example, preferably starting from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[1156] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and further preferably 15 to 240 minutes.

[1157] In particular, when a multilayer laminate is formed, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, and particularly preferably 120° C. or higher from the viewpoint of interlayer adhesion.

[1158] The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and further preferably 240°C or lower.

[1159] Heating can be performed in stages. As an example, the following process can be performed: heating from 25°C to 120°C at 3°C / min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C / min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to treat while irradiating with ultraviolet rays. The properties of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be set as a process of more than two stages, for example, the first stage pretreatment process can be performed in the range of 100 to 150°C, and then the second stage pretreatment process can be performed in the range of 150 to 200°C.

[1160] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[1161] The heating step is preferably performed in a low oxygen concentration environment such as by flowing an inert gas such as nitrogen, helium, or argon under reduced pressure from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[1162] The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[1163] <Exposure Step after Development>

[1164] The pattern obtained by the development step (the pattern after the rinse step when the rinse step is performed) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.

[1165] That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step.

[1166] In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor or the like by photosensitization of a photobase generator, a detachment reaction of an acid-decomposable group by photosensitization of a photoacid generator, and the like can be promoted.

[1167] In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, but it is preferred that the entire pattern be exposed.

[1168] The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. 2 , more preferably 100 to 15,000 mJ / cm 2 .

[1169] The post-development exposure step can be performed, for example, using the light source in the above-mentioned exposure step, and preferably using broadband light.

[1170] <Metal Layer Formation Step>

[1171] The pattern obtained in the development step (preferably the pattern provided to at least one of the heating step and the post-development exposure step) may be provided to the metal layer forming step of forming a metal layer on the pattern.

[1172] That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained in the developing step (preferably a pattern provided to at least one of the heating step and the post-development exposure step).

[1173] The metal layer is not particularly limited, and any existing metal types can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

[1174] The formation method of metal layer is not particularly limited, and existing methods can be used. For example, the method described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift off, electroplating, electroless plating, etching, printing and the method of combining these etc. can be considered. More specifically, the patterning method of combining sputtering, photolithography and etching, the patterning method of combining photolithography and electroplating can be enumerated. As the preferred mode of plating, the electroplating using copper sulfate plating solution or copper cyanide plating solution can be enumerated.

[1175] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

[1176] <Purpose>

[1177] As the fields to which the manufacturing method of the cured product of the present invention or the cured product can be applied, the insulating film of electronic devices, the interlayer insulating film for the redistribution layer, the stress buffer film, etc. can be cited. In addition, the sealing film, the substrate material (the base film or cover film of the flexible printed circuit board, the interlayer insulating film) or the case where a pattern is formed on the insulating film for the installation purpose of the above-mentioned by etching can be cited. For these uses, for example, reference can be made to Scierce & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaaki / Supervision, CMC Technology Library "Basics and Development of Polyimide Materials" issued in November 2011, Japan Polyimide Aromatic Polymer Research Association / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[1178] 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 or screen printing plates, for etching of molded parts, and for the production of protective varnishes and dielectric layers in electronics, especially micro...

Claims

1. A resin composition comprising: At least one resin selected from polyimide and its precursor; polymerizable compounds; and Photopolymerization initiator, The ethylenically unsaturated bond equivalent in the polymerizable compound is 100 g / mol to 300 g / mol.

2. The resin composition according to claim 1, in, The polymerizable compound is a polymerizable compound having two ethylenically unsaturated bonds.

3. The resin composition according to claim 1, in, The polymerizable compound is di(meth)acrylate.

4. The resin composition according to claim 1, in, The polymerizable compound is diacrylate.

5. The resin composition according to claim 1, in, The polymerizable compound is a compound including a linear aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group and a polymerizable group.

6. A resin composition comprising: At least one resin selected from polyimide and its precursor; A polymerizable compound represented by the following formula (1); and Photopolymerization initiator, When n is 1, L 1 represents a monovalent aliphatic hydrocarbon group in which a hydrogen atom is optionally substituted, and when n is 2 or more, L 1 represents an n-valent hydrocarbon group in which the hydrogen atom is optionally substituted and which contains a structure represented by the following formula (L-1), or a structure represented by the following formula (L-2), R P represents a polymerizable group, n represents an integer greater than 1, In formula (L-1), R L Each independently represents a hydrogen atom or a monovalent substituent, and * each independently represents a P The bonding position of the structure of L At least two of are optionally bonded to form a ring structure, In formula (L-2), L Z1 and L Z2 Each independently represents a hydrocarbon group in which the hydrogen atom is optionally substituted, R each independently represents a substituent, a each independently represents an integer of 0 to 4, and * represents the same as R in formula (1-1). P bonding position.

7. The resin composition according to claim 6, in, The L 1 It is a straight-chain or cyclic hydrocarbon group.

8. The resin composition according to claim 6, in, The n is 2.

9. The resin composition according to claim 6, in, The R P It is a (meth)acryloyloxy group.

10. The resin composition according to claim 6, in, The L 1 It is an aliphatic hydrocarbon group.

11. The resin composition according to any one of claims 1 to 10, in, The resin has a group formed by removing two or more hydrogen atoms from a structure represented by the following formula (A-1), In formula (A-1), A 1 ~A 3 Each independently represents a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

12. The resin composition according to any one of claims 1 to 10, in, The weight average molecular weight of the resin is 20,000 or less.

13. The resin composition according to any one of claims 1 to 10, in, The resin is polyimide. 14 . The resin composition according to claim 1 , further comprising a solvent containing a ketone structure. 15 . The resin composition according to claim 1 , further comprising a light absorber.

16. The resin composition according to claim 15, in, The light absorber is naphthoquinone diazide. 17 . A cured product obtained by curing the resin composition according to claim 1 . 18 . The cured product according to claim 17 , which has a dielectric loss tangent of 0.01 or less at 28 GHz. 19 . A laminate comprising two or more layers consisting of the cured product according to claim 17 , wherein a metal layer is included between any of the layers consisting of the cured product.

20. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 10 to form a film on a substrate.

21. The method for producing a cured product according to claim 20, wherein include: An exposure step of selectively exposing the film; and a developing step of developing the film using a developer to form a pattern. 22 . The method for producing a cured product according to claim 20 , comprising a heating step of heating the film at 50° C. to 450° C.

23. A method for producing a laminate, comprising the method for producing a cured product according to claim 20.

24. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 20.

25. A semiconductor device comprising the cured product according to claim 17.

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