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

Abstract

The invention provides 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 contains: at least one resin selected from the group consisting of polyimides and polyimide precursors having polymerizable groups; and a compound B1 represented by formula (1-1) in which R1 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms, Ar1 represents an optionally substituted aromatic group, Z represents a hydrogen atom or an n-valent organic group, and Z does not contain a structure of-X1-C (= 0)-C (= 0)-X2-, the ethylenically unsaturated bond valence of compound B1 being 3.0 mmol / g or more. # imgabs0 #

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, technologies using resin materials made from resin compositions containing resins are being utilized.

[0003] For example, cyclized resins such as polyimide are suitable for various uses because of their excellent heat resistance and insulation properties. As the above uses, there is no particular limitation. Taking a semiconductor device for mounting as an example, examples include use as a material for an insulating film, a sealant, or a protective film. Further, it can also be used as a base film, a cover film, etc. of a flexible substrate.

[0004] For example, in the above uses, cyclized resins such as polyimide are used in the form of polyimide or a resin composition containing a polyimide precursor.

[0005] Such a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed, whereby a cured product can be formed on the substrate.

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

[0007] Since the resin composition can be applied by a known coating method or the like, it can be said that the adaptability in manufacturing is excellent. For example, the resin composition to be applied has a high degree of freedom in design such as the shape, size, and application position at the time of application. From the viewpoint that, in addition to the high performance of polyimide, such adaptability in manufacturing is also excellent, the above resin composition is increasingly expected to be developed for industrial applications.

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

[0009] Patent Document 2 describes a curable resin composition containing at least one resin selected from a polyimide precursor and a polybenzoxazole precursor; and Compound B having at least one structure selected from an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure, and an oxalic acid ester amide structure and a polymerizable group.

[0010] Prior Art Documents

[0011] Patent document

[0012] Patent document 1: Japanese Patent Application Laid-Open No. 2021-196482

[0013] Patent document 2: WO 2022 / 045060 Summary of the invention

[0014] Technical problem to be solved by the invention

[0015] In a resin composition for obtaining a cured product, it is required that the cured product obtained has a small coefficient of thermal expansion.

[0016] By having a small coefficient of thermal expansion, various advantages such as improved reliability of the operation of semiconductor devices under high-temperature conditions and low-temperature conditions can be achieved, for example.

[0017] An object of the present invention is to provide a resin composition capable of obtaining a cured product with a small coefficient of thermal expansion, 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.

[0018] Means for solving the technical problem

[0019] Hereinafter, examples of representative embodiments of the present invention are shown.

[0020] <1>A resin composition containing:

[0021] At least one resin selected from polyimide and a polyimide precursor having a polymerizable group; and

[0022] A compound B1 represented by the following formula (1-1),

[0023] The ethylenically unsaturated bond valence of the above compound B1 is 3.0 mmol / g or more.

[0024] [Chemical formula 1]

[0025]

[0026] In formula (1-1), R 1 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar 1 Each independently represents an aromatic group which may have a substituent, Z represents a hydrogen atom or an n-valent organic group, and Z does not contain -X 1 -C(=O)-C(=O)-X 2 -such a structure, X 1 and X2 Each independently represents -O- or -NH-, n represents an integer of 1 to 6, m represents 1 or 2, when n is 1, m is 2 and Z is a hydrogen atom, when n is an integer of 2 to 6, Z represents an n-valent organic group, Z and Ar 1 It is a structure having no ethylenically unsaturated bond.

[0027] <2> according to <1> The resin composition, wherein

[0028] R in formula (1-1) 1 is a hydrogen atom and Ar 1 It is an aromatic hydrocarbon group which may have a substituent.

[0029] <3> according to <1> or <2> The resin composition contains two or more compounds B1, or contains compound B1 and a polymerizable compound different from compound B1.

[0030] <4> according to <1> to <3> The resin composition described in any one of the preceding claims, wherein

[0031] The molecular weight of the compound B1 is 2,000 or less.

[0032] <5> A resin composition comprising:

[0033] At least one resin selected from the group consisting of polyimide and a polyimide precursor having a polymerizable group; and

[0034] Compound B2 represented by the following formula (1-2).

[0035] [Chemical formula 2]

[0036]

[0037] In formula (1-2), L 1 ~L 3 Each independently represents a divalent linking group having no aromatic ring structure, R a Each independently represents a hydrogen atom or a monovalent organic group.

[0038] <6> according to <1> to <5> The resin composition described above further comprises an azole compound.

[0039] <7> according to <1> to <6> The resin composition described in any one of the above is used for forming an interlayer insulating film for a redistribution layer.

[0040] <8> A solidified material, which is solidified <1> to <7> The resin composition described in any one of the above.

[0041] <9>A laminate including two or more layers made of the cured product described in <8>, and including a metal layer between any two layers made of the cured product.

[0042] <10>A method for producing a cured product, including a film forming step of applying the resin composition according to any one of <1> to <7> onto a substrate to form a film.

[0043] <11>The method for producing a cured product according to <10>, including:

[0044] An exposure step of selectively exposing the film; and

[0045] A development step of developing the film with a developer to form a pattern.

[0046] <12>The method for producing a cured product according to <10> or <11>, including a heating step of heating the film.

[0047] <13>A method for producing a laminate, including the method for producing a cured product according to any one of <10> to <12>.

[0048] <14>A method for producing a semiconductor device, including the method for producing a cured product according to any one of <10> to <12>.

[0049] <15>A semiconductor device containing the cured product described in <8>.

[0050] Advantages of the Invention

[0051] According to the present invention, there is provided a resin composition capable of obtaining a cured product with a small coefficient of thermal expansion, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device containing the cured product. Detailed Embodiments

[0052] Hereinafter, main embodiments of the present invention will be described. In addition, the present invention is not limited to the disclosed embodiments.

[0053] In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively.

[0054] In this specification, the term "step" means not only an independent step, but also a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved.

[0055] In the notations of groups (atomic groups) in this specification, the notations without substitution or unsubstitution marks include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl without substituents (unsubstituted alkyl) but also alkyl with substituents (substituted alkyl).

[0056] 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. And as the light used for exposure, there can be mentioned the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiations.

[0057] In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either one of them, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid" or either one of them, and "(meth)acryloyl" means both "acryloyl" and "methacryloyl" or either one of them.

[0058] In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0059] In this specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. And in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0060] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by the gel permeation chromatography (GPC) method and are defined as polystyrene conversion values. In this specification, for example, using HLC - 8220GPC (manufactured by TOSOH CORPORATION), by connecting the guard columns HZ - L, TSKgel Super HZM - M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all of the above are manufactured by TOSOH CORPORATION) in series as the column, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, in cases where the solubility is low and THF is not suitable as the eluent, NMP (N - methyl - 2 - pyrrolidone) can also be used. And unless otherwise specified, the detection in GPC measurement uses a UV ray (ultraviolet ray) detector with a wavelength of 254 nm.

[0061] In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", as long as there is another layer above or below the layer serving as the reference among the multiple layers of interest. That is, a third layer or a third element may be further interposed between the layer serving as the reference and the other layer, and the layer serving as the reference and the other layer do not need to be in contact. Unless otherwise specifically stated, the direction of the substrate stacking layer is referred to as "upper", or when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". In addition, this setting of the up and down directions is for the convenience of explaining this specification. In actual practice, the "upper" direction in this specification may also be different from the vertically upward direction.

[0062] In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds belonging to that component. And, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to that component.

[0063] In this specification, unless otherwise specified, the temperature is 23 °C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0064] In this specification, a combination of preferred modes is a more preferred mode.

[0065] (Resin composition)

[0066] The resin composition according to the first aspect of the present invention (hereinafter, also referred to as "the first resin composition") contains: at least one resin selected from polyimide and a polyimide precursor having a polymerizable group; and a compound B1 represented by the following formula (1-1), and the ethylenic unsaturated bond valence of the compound B1 is 3.0 mmol / g or more.

[0067] [Chemical formula 3]

[0068]

[0069] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar 1 each independently represents an aromatic group which may have a substituent, Z represents a hydrogen atom or an n-valent organic group, and Z does not contain -X 1 -C(=O)-C(=O)-X 2 - such a structure, X 1 and X 2Each independently represents -O- or -NH-, n represents an integer of 1 to 6, m represents 1 or 2. When n is 1, m is 2 and Z is a hydrogen atom. When n is an integer of 2 to 6, Z represents an n-valent organic group.

[0070] The resin composition according to the second aspect of the present invention (hereinafter, also referred to as "second resin composition") contains at least one resin selected from polyimide and a polyimide precursor having a polymerizable group; and a compound B2 represented by the following formula (1-2).

[0071] [Chemical formula 4]

[0072]

[0073] In formula (1-2), L 1 ~L 3 Each independently represents a divalent linking group having no aromatic ring structure, and R a Each independently represents a hydrogen atom or a monovalent organic group.

[0074] Hereinafter, the first resin composition and the second resin composition are also simply collectively referred to as "resin composition".

[0075] And, compound B1 and compound B2 are also simply collectively referred to as compound B.

[0076] The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and preferably used for forming a film for exposure and development using a developer containing an organic solvent.

[0077] The resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.

[0078] Moreover, the resin composition of the present invention can be used to form a positive-type developing photosensitive film and can also be used to form a negative-type developing photosensitive film.

[0079] In the present invention, negative-type development means development in which non-exposed portions are removed by development during exposure and development, and positive-type development means development in which exposed portions are removed by development.

[0080] As the above exposure method, the above developer, and the above development method, for example, the exposure method described in the exposure step in the description of the method for manufacturing a cured product described below, the developer and the development method described in the development step can be used.

[0081] According to the resin composition of the present invention, a cured product having a small coefficient of thermal expansion (CTE) can be obtained.

[0082] The mechanism for obtaining the above effects is not yet clear, but the speculation is as follows.

[0083] The first resin composition contains compound B1.

[0084] Herein, by the polymerization of the vinyl group described in the structure represented by the first formula (1-1) in compound B1, the mobility of the resin (or, crosslinked body containing the resin) in the film is reduced, and thus it is considered that the CTE is reduced.

[0085] Moreover, compound B1 does not contain -X 1 -C(=O)-C(=O)-X 1 - such a structure (X 1 、X 2 is -O- or -NH-), and thus it is considered that it is difficult to cause the decomposition of such a structure based on heat and the CTE is reduced.

[0086] In addition, the resin composition of the present invention contains polyimide, or a polyimide precursor containing a polymerizable group.

[0087] In the case of using a polyimide precursor, it is considered that the polymerization between the polymerizable group in the polyimide precursor and compound B1 is easy to proceed, and it is easy to form a crosslinked body formed by the resin and compound B1, and the CTE is more easily reduced.

[0088] In addition, compared with the case of using only a polymerizable compound having a methacryloyloxy group used in the past, by using compound B1 having a low-polarity structure, the cured product can be made to have a lower dielectric constant and a lower dielectric loss tangent.

[0089] Furthermore, it is considered that by not containing -X 1 -C(=O)-C(=O)-X 1 - and other high-polarity structures, the cured product is further made to have a lower dielectric constant and a lower dielectric loss tangent.

[0090] The second resin composition contains compound B2.

[0091] Compound B2 has an isocyanuric acid ring structure.

[0092] This isocyanuric acid ring structure easily interacts with the above resin in the cured product, and the mobility of the resin is reduced, and thus it is considered that the CTE of the film is easily reduced.

[0093] Moreover, it is considered that the isocyanuric acid ring structure is not easily decomposed by heat and the CTE is reduced.

[0094] In addition, the resin composition of the present invention contains polyimide, or a polyimide precursor containing a polymerizable group.

[0095] In the case of using a polyimide precursor, it is considered that the polymerization between the polymerizable group in the polyimide precursor and compound B2 is easy to proceed, and it is easy to form a crosslinked body formed by the resin and compound B2, and the CTE is more likely to be reduced.

[0096] In addition, compared with the case of using only the polymerizable compound having a methacryloxy group used in the past, by using compound B2 having a low-polarity structure, it is possible to achieve a low dielectric constant and a low dielectric loss tangent of the cured product.

[0097] Here, a composition containing compound B is not described in Patent Document 1 and Patent Document 2.

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

[0099] <Specific Resin>

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

[0101] A polyimide precursor refers to a resin that becomes a polyimide by generating a chemical structure change by an external stimulus, preferably a resin that becomes a polyimide by generating a chemical structure change by heat, and more preferably a resin that forms a ring structure by a ring-closing reaction by heat to become a polyimide.

[0102] The polyimide precursor preferably has a polymerizable group and contains a radical polymerizable group.

[0103] The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy group, oxetanyl, benzoxazolyl, blocked isocyanate group, and amino group. As the polymerizable group of the polyimide precursor, a group having an ethylenic unsaturated bond is preferred.

[0104] Examples of the group having an ethylenic unsaturated bond include vinyl, allyl, isopropyl, 2-methylallyl, a group having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl, etc.), (meth)acrylamide group, (meth)acryloxy group, etc. A group having an aromatic ring directly bonded to vinyl or (meth)acryloxy group is preferred, and (meth)acryloxy group is more preferred.

[0105] The polyimide preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0106] The preferred form of the polymerizable group in the polyimide is the same as that of the polymerizable group in the above-mentioned polyimide precursor.

[0107] When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator. In addition, a sensitizer can be contained as needed. A negative photosensitive film is formed from such a resin composition, for example.

[0108] The value of the polymerizable group in the specific resin (total molar amount of the polymerizable group relative to 1 g of the specific resin) is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0109] The specific resin preferably has a group formed by removing two or more hydrogen atoms from the structure represented by the following formula (A-1), and more preferably has a group formed by removing two or more hydrogen atoms from the structure represented by the following formula (A-2).

[0110] [Chemical formula 5]

[0111]

[0112] In formula (A-1), A 1 ~A 3 are each independently a single bond or a divalent linking group, and the four benzene rings described in formula (A-1) may each have a substituent.

[0113] A 1 ~A 3 are 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)-, -NHC(=O)-, or a group composed of two or more combinations 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 composed of two or more combinations thereof, and still more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-. 2 1

[0114] In particular, A 1 and A 3 are preferably -O-.

[0115] In particular, A 2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.

[0116] Among them, A 1 and A 3 are -O- and A 2 is -C(CH 3 ) 2- is also one of the preferred modes of the present invention.

[0117] The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted by a fluorine atom is not particularly limited, preferably 1 to 6, more preferably 1 to 4.

[0118] As specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted by a fluorine atom, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - etc. can be cited. Among them, -C(CH 3 ) 2 - is preferred.

[0119] As substituents in the 4 benzene rings described in formula (A-1), a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom can be substituted by a fluorine atom, etc. can be cited.

[0120] Moreover, the mode in which all 4 benzene rings described in formula (A-1) are unsubstituted is also one of the preferred modes of the present invention.

[0121] Moreover, the specific resin preferably contains the structure represented by formula (A-1) as R 115 or R 111 in formula (2) described later, or R 131 or R 132 in formula (4). These modes will be described later.

[0122] Specific examples of the structure represented by formula (A-1) are described below, but the present invention is not limited to these.

[0123] [Chemical formula 6]

[0124]

[0125] [Polyimide precursor]

[0126] The type etc. of the polyimide precursor used in the present invention are not particularly limited, but preferably contain a repeating unit represented by the following formula (2).

[0127] [Chemical formula 7]

[0128]

[0129] In formula (2), A 1 and A 2 each independently represent an oxygen atom or -NR z -, R 111 represents a divalent organic group, R 115represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0130] A in formula (2) 1 and A 2 each independently represents an oxygen atom or -NR z -, preferably an oxygen atom.

[0131] R z represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0132] R in formula (2) 111 represents a divalent organic group. As the divalent organic group, examples thereof include linear or branched aliphatic groups, cycloaliphatic groups, and groups containing aromatic groups. Preferred are linear or branched aliphatic groups having 2 to 20 carbon atoms, cycloaliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or groups composed of combinations thereof. More preferred are groups containing aromatic groups having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the above cycloaliphatic group and aromatic group may be substituted with a group containing a heteroatom. As an example of R 111 in formula (2), groups represented by -Ar- and -Ar-L-Ar- can be cited, and groups represented by -Ar-L-Ar- are preferred. Among them, Ar is each independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, or -NHCO- or a group composed of a combination of two or more of the above. The preferred ranges of these are as described above.

[0133] R 111 is preferably derived from a diamine. As the diamine used in the production of the polyimide precursor, linear or branched aliphatic, cycloaliphatic, or aromatic diamines, etc. can be cited. Only one kind of diamine may be used, or two or more kinds may be used.

[0134] Specifically, R 111Preferably a diamine having a linear or branched aliphatic group having 2 to 20 carbon atoms, a cycloaliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination thereof, more preferably a diamine having 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 of the ring member of the cycloaliphatic group and the aromatic group may be substituted with a group containing a heteroatom. Examples of the group having an aromatic group include the following groups.

[0135] [Chemical formula 8]

[0136]

[0137] In the formula, A is a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -SO 2 -, -NHCO-, or a group in these combinations, more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, or -SO 2 -, and further preferably -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 -, or -C(CH 3 ) 2 -.

[0138] In the formula, * represents the bonding position with other structures.

[0139] Specific examples of the diamine include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane;

[0140] 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 isophorone diamine;

[0141] 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'-diaminodiphenyl sulfone, 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)-10H-anthracene, 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, guanylamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,At least one diamine selected from 5-bis(4-aminophenyl) decafluoropentane, 1,7-bis(4-aminophenyl) tetrafluorooctane, 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, 4,4'-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'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

[0142] Moreover, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferably used.

[0143] Moreover, 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.

[0144] From the viewpoint of the flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Herein, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 -, or -NHCO- or a group composed 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 by a fluorine atom, -O-, -CO-, -S- or -SO 2 -. The aliphatic hydrocarbon group herein is preferably an alkylene group.

[0145] Moreover, from the viewpoint of the i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of the i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferable.

[0146] Formula (51)

[0147] [Chemical Formula 9]

[0148]

[0149] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 ~R 57 is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents the bonding position to the nitrogen atom in formula (2).

[0150] As the monovalent organic group for R 50 ~R 57 , unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. can be mentioned.

[0151] [Chemical Formula 10]

[0152]

[0153] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents the bonding position to the nitrogen atom in formula (2).

[0154] As the diamine that imparts the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. can be mentioned. These can be used alone or in combination of two or more.

[0155] Moreover, R 111 is also preferably a group represented by the following formula (71). In the above manner, R 111 is more preferably a group represented by the following formula (72).

[0156] 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).

[0157] [Chemical Formula 11]

[0158]

[0159] In formula (71), A 1 ~A 3Each is independently a single bond or a divalent linking group. * represents the bonding position to the nitrogen atom in formula (2). The four benzene rings described in formula (71) may each have a substituent.

[0160] In formula (72), * represents the bonding position to the nitrogen atom in formula (2).

[0161] In formula (71), A 1 ~A 3 and the preferred modes of the substituents in the benzene ring are the same as those of A 1 ~A 3 and the benzene ring in formula (A-1) above.

[0162] R in formula (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0163] In formula (5) or formula (6), * each independently represents the bonding position to other structures.

[0164] [Chemical formula 12]

[0165]

[0166] In formula (5), R 112 is a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO 2 -, and -NHCO-, and groups in combinations thereof, more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, and -SO 2 -, and further preferably a divalent group selected from -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.

[0167] Also, R 115 is also preferably a group represented by the following formula (7). In the above mode, R 111 is more preferably a group represented by the following formula (7-2).

[0168] Formula (7) is a group formed by removing 4 hydrogen atoms from the structure represented by formula (A-1) above, and formula (7-2) is a group formed by removing 4 hydrogen atoms from the structure represented by formula (A-2) above.

[0169] [Chemical Formula 13]

[0170]

[0171] In formula (7), A 1 ~A 3 are each 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.

[0172] In this specification, a bond crossing the side of a ring structure means substituting any one of the hydrogen atoms in its ring structure.

[0173] In formula (7-2), * represents the bonding position to the carbonyl group in formula (2).

[0174] In formula (7), A 1 ~A 3 and the preferred modes of the substituents in the benzene ring are the same as those of A 1 ~A 3 and the substituents in the benzene ring in the above formula (A-1).

[0175] Regarding R 115 , specifically, examples include tetracarboxylic acid residues remaining after removing the anhydride groups from tetracarboxylic dianhydrides. As the structure corresponding to R 115 , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or may contain two or more types of tetracarboxylic dianhydride residues.

[0176] The tetracarboxylic dianhydride is preferably represented by the following formula (0).

[0177] [Chemical Formula 14]

[0178]

[0179] In formula (0), R 115 represents a tetravalent organic group. The meaning of the preferred range of R 115 is the same as the meaning of R 115 in formula (2), and the preferred ranges are also the same.

[0180] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide 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-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0181] Moreover, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be cited as preferred examples.

[0182] In formula (2), at least one of R 111 and R 115 may also have an OH group. More specifically, as R 111 , a residue of a diaminophenol derivative can be cited.

[0183] R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group is preferably included. Moreover, it is preferred that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferred that both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. The preferred form of the polymerizable group is as described above.

[0184] Among them, it is preferred that R 113 and R114 At least one of them contains a group represented by the following formula (III).

[0185] [Chemical formula 15]

[0186]

[0187] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

[0188] In formula (III), * represents the bonding position with other structures.

[0189] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkyleneoxy group.

[0190] Preferred examples of R 201 include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butylene, 1,3-butylene, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy groups, more preferably alkylene groups such as ethylene and propylene, -CH 2 CH(0H)CH 2 -, cyclohexyl, polyalkyleneoxy groups, and even more preferably alkylene groups such as ethylene and propylene or polyalkyleneoxy groups.

[0191] 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 multiple alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0192] When the polyalkyleneoxy group contains a plurality of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as an alternating pattern.

[0193] The carbon atom number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon atom number of the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, still further preferably 2 to 4, still further preferably 2 or 3, and particularly preferably 2.

[0194] Moreover, the above-mentioned alkylene group may have a substituent. Preferred substituents include an alkyl group, an aryl group, a halogen atom, etc.

[0195] Moreover, the number of alkyleneoxy groups contained in the polyalkyleneoxy (the repeating number of the polyalkyleneoxy) is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 6.

[0196] As the polyalkyleneoxy, from the viewpoints of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, polyethyleneoxy or polypropyleneoxy is more preferred, and polyethyleneoxy is still more preferred. 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 randomly arranged, may be arranged in blocks, or may be arranged in a pattern such as an alternating pattern. The preferred manner of the repeating number of ethyleneoxy groups and the like in these groups is as described above.

[0197] In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. As an example of such a tertiary amine compound having an ethylenically unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

[0198] In formula (2), at least one of R 113 and R 114 can be a polarity-converting group such as an acid-decomposable group. As the acid-decomposable group, as long as it decomposes by the action of an acid to generate a base-soluble group such as a phenolic hydroxyl group or a carboxyl group, it is not particularly limited, and an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and an acetal group or a ketal group is more preferred from the viewpoint of exposure sensitivity.

[0199] As specific examples of the acid-decomposable group, tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuryl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether group, etc. can be cited. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuryl is preferred.

[0200] The polyimide precursor also preferably has a fluorine atom 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.

[0201] Moreover, for the purpose of improving the adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, a method using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be cited.

[0202] The repeating unit represented by formula (2) is preferably the 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 the repeating unit represented by formula (2-A). By containing the repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased.

[0203] Formula (2-A)

[0204] [Chemical formula 16]

[0205]

[0206] In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

[0207] A 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferably the same range. R 112 has the same meaning as R 112 in formula (5), and preferably the same range.

[0208] The polyimide precursor may contain one kind of repeating unit represented by formula (2), or may contain two or more kinds. And it may include structural isomers of the repeating unit represented by formula (2). In addition to containing the repeating unit represented by formula (2) above, the polyimide precursor may also contain other kinds of repeating units.

[0209] As one embodiment of the polyimide precursor in the present invention, a mode in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units can be cited. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal ones can be the repeating unit represented by formula (2).

[0210] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.

[0211] The dispersity of the molecular weight of the above polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit value of the dispersity of the molecular weight of the polyimide precursor is not particularly limited. For example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less.

[0212] In this specification, the dispersity of the molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight.

[0213] When the resin composition contains various polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. Moreover, the weight-average molecular weight, number-average molecular weight, and dispersity calculated by regarding the above various polyimide precursors as one resin are preferably within the above ranges, respectively.

[0214] 〔Polyimide〕

[0215] 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.

[0216] In this specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formability, it is preferably a polyimide that dissolves 0.5 g or more, and still more preferably a polyimide that dissolves 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, and it is preferably 100 g or less.

[0217] From the viewpoints of the 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.

[0218] -fluorine atom-

[0219] From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has a fluorine atom.

[0220] The fluorine atom is preferably included in, for example, R in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4)131 Among them, R which is more preferably included as a fluoroalkyl group in the repeating unit represented by the following formula (4) 132 or R in the repeating unit represented by the following formula (4) 131 .

[0221] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0222] -silicon atom-

[0223] From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has a silicon atom.

[0224] The silicon atom is preferably included, for example, in R in the repeating unit represented by the following formula (4) 131 Among them, it is more preferably included as an organically modified (poly)siloxane structure in R in the repeating unit represented by the following formula (4) 131 .

[0225] The above-mentioned silicon atom or the above-mentioned organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.

[0226] The amount of the silicon atom relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0227] -olefinic unsaturated bond-

[0228] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an olefinic unsaturated bond.

[0229] The polyimide may have an olefinic unsaturated bond at the main chain end or may have an olefinic unsaturated bond in the side chain, and preferably has it in the side chain.

[0230] The above-mentioned olefinic unsaturated bond preferably has radical polymerizability.

[0231] The olefinic unsaturated bond is preferably included in R in the repeating unit represented by the following formula (4) 132 or R 131 Among them, it is more preferably included as a group having an olefinic unsaturated bond in R 132 or R 131 .

[0232] Among them, the olefinic unsaturated bond is preferably included in R in the repeating unit represented by the following formula (4) 131 Among them, it is more preferably included as a group having an olefinic unsaturated bond in R 131 .

[0233] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group and other vinyl groups which are directly bonded to an aromatic ring and may be substituted, a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (IV), etc.

[0234] [Chemical formula 17]

[0235]

[0236] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

[0237] 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 alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3 carbon atoms; the repeating number of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3) or a group formed by combining two or more of them.

[0238] Examples of the alkylene group having 2 to 12 carbon atoms include any of a linear, branched, cyclic alkylene group or an alkylene group represented by a combination thereof.

[0239] Examples of the alkylene group having 2 to 12 carbon atoms preferably include an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.

[0240] Among them, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).

[0241] [Chemical formula 18]

[0242]

[0243] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms or a group formed by bonding two or more of them, X represents an oxygen atom or a sulfur atom, * represents a bonding position with other structures, and ● represents a bonding position of the oxygen atom bonded to R 21 in formula (IV).

[0244] In formulas (R1) to (R3), the preferred mode 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 R21 The preferred modes of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same.

[0245] In formula (R1), X is preferably an oxygen atom.

[0246] In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred modes are also the same.

[0247] The structure represented by formula (R1) can be obtained, for example, 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, etc.).

[0248] The structure represented by 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, etc.).

[0249] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

[0250] In formula (IV), * represents the bonding position with other structures, and is preferably the bonding position with the main chain of the polyimide.

[0251] The amount of the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0252] - Polymerizable group other than the group having an ethylenically unsaturated bond -

[0253] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0254] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include cyclic ether groups such as epoxy group and oxetanyl group, alkoxymethyl groups such as methoxymethyl group, and hydroxymethyl group.

[0255] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained, for example, in R in the repeating unit represented by formula (4) described later. 131 in.

[0256] The amount of the polymerizable group other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0257] -Polarity conversion group-

[0258] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R in the above formula (2) 113 and R 114 and the preferred modes are also the same.

[0259] The polarity conversion group is included, for example, in R in the repeating unit represented by the following formula (4) 131 , R 132 , the ends of the polyimide, etc.

[0260] -Acid value-

[0261] When the polyimide is used for alkali development, from the viewpoint of improving the developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.

[0262] The above acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and still more preferably 200 mgKOH / g or less.

[0263] When the polyimide is used in the development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and still more preferably 5 to 20 mgKOH / g.

[0264] The above acid value is measured by a known method. For example, it is measured by the method described in JIS K 0070:1992.

[0265] As the acid group contained in the polyimide, from the viewpoint of balancing the storage stability and the developability, the acid group with a pKa of preferably 0 to 10, more preferably 3 to 8 is preferred.

[0266] pKa is the value of the equilibrium constant Ka obtained by considering the dissociation reaction in which the acid releases hydrogen ions and expressing it as the negative common logarithm pKa. In this specification, unless otherwise specifically stated, pKa is set as the calculated value based on ACD / ChemSketch (registered trademark). pKa can refer to the values described in "Revised 5th Edition Chemistry Handbook Basic Volume" edited by the Chemical Society of Japan.

[0267] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0268] As such an acid group, the polyimide preferably contains at least 1 selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0269] - phenolic hydroxyl group -

[0270] From the viewpoint of appropriately adjusting the development rate based on an alkali developer, the polyimide preferably has a phenolic hydroxyl group.

[0271] The polyimide may have a phenolic hydroxyl group at the main chain end or may have a phenolic hydroxyl group in the side chain.

[0272] The phenolic hydroxyl group is preferably included, for example, in R in the repeating unit represented by the following formula (4). 132 or R 131 .

[0273] 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.

[0274] The polyimide used in the present invention is not particularly limited as long as it is a high molecular compound having an imide structure, and preferably contains a repeating unit represented by the following formula (4).

[0275] [Chemical formula 19]

[0276]

[0277] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.

[0278] In the case of having a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132 , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide.

[0279] Formula (4-1)

[0280] [Chemical formula 20]

[0281]

[0282] In formula (4-1), R 133 is a polymerizable group, and the meanings of the other groups are the same as those in formula (4).

[0283] Formula (4-2)

[0284] [Chemical formula 21]

[0285]

[0286] R 134 and R 135At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group. The meanings of the other groups are the same as those in formula (4).

[0287] As the polymerizable group, the above-mentioned groups containing an ethylenically unsaturated bond or the above-mentioned crosslinkable groups other than the groups having an ethylenically unsaturated bond can be mentioned.

[0288] R 131 represents a divalent organic group. As the divalent organic group, those the same as R in formula (2) can be exemplified, and the preferred ranges are also the same. 111 The same and the preferred ranges are also the same.

[0289] As R 131 , a diamine residue remaining after removing the amino group of diamine can be mentioned. As the diamine, aliphatic, cycloaliphatic or aromatic diamine etc. can be mentioned. As a specific example, the example of R in formula (2) of the polyimide precursor can be mentioned. 111 The example.

[0290] From the viewpoint of more effectively suppressing warping during calcination, R 131 is preferably a diamine residue having at least 2 alkylene glycol units in the main chain. More preferably, it is a diamine residue containing a total of 2 or more of any one or both of ethylene glycol chains and propylene glycol chains in one molecule, and further preferably the above-mentioned diamine and a diamine residue not containing an aromatic ring.

[0291] As the diamine containing a total of 2 or more of any one or both of ethylene glycol chains and propylene glycol chains in one molecule, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine etc. can be mentioned, but are not limited to these.

[0292] R 132 represents a tetravalent organic group. As the tetravalent organic group, those the same as R in formula (2) can be exemplified, and the preferred ranges are also the same. 115 The same and the preferred ranges are also the same.

[0293] For example, the 4 bonding groups of the tetravalent organic group exemplified as R 115 are bonded to the 4 -C(=O)- parts in formula (4) to form a condensed ring.

[0294] R 132Examples include tetracarboxylic acid residues remaining after removing the anhydride groups from tetracarboxylic dianhydrides. As a specific example, R in formula (2) of the polyimide precursor can be cited. 115 From the perspective of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0295] It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , examples include 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) as preferred examples. As R 132 , examples include the above (DAA-1) to (DAA-5) as more preferred examples.

[0296] Moreover, the polyimide also preferably contains a repeating unit represented by the following formula (4-3) as the repeating unit represented by formula (4).

[0297] [Chemical formula 22]

[0298]

[0299] In formula (4-3), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group having 4 or more carbon atoms, and 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 more.

[0300] [Chemical formula 23]

[0301]

[0302] In formula (R-1), L 1 represents an a2+1 valent linking group, A 1 represents a polymerizable group, a2 represents an integer of 1 or more, and * represents the bonding position to X 1 or Y 1 in formula (4-3).

[0303] -R 1 -

[0304] R 1 each independently represents a structure represented by formula (R-1).

[0305] In formula (R-1), L 1 represents a divalent linking group with a valence of a2 + 1.

[0306] L 1 is preferably a group represented by the following formula (L-1).

[0307] [Chemical formula 24]

[0308]

[0309] In formula (L-1), L x represents a divalent linking group with a valence of a2 + 1, a2 represents an integer of 1 or more, * represents the bonding position with X in formula (4-3) 1 or Y 1 and # represents the bonding position with Z in formula (R-1). 1

[0310] L x is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0311] The preferred mode of a2 in formula (L-1) is the same as the preferred mode of a2 in formula (R-1).

[0312] -A 1 -

[0313] A in formula (R-1) 1 represents a polymerizable group, and the preferred mode of the polymerizable group is the same as the preferred mode of the polymerizable group in the above-mentioned specific resin.

[0314] Among them, at least one of A in formula (R-1) contained in formula (4-3) 1 is preferably a group having an aromatic ring directly bonded to a vinyl group, (meth)acrylamide group, or (meth)acryloyloxy group, and more preferably vinylphenyl.

[0315] -a2-

[0316] In formula (R-1), a2 represents an integer of 1 or more, preferably 1 or 2, and still more preferably 1.

[0317] And the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0318] -X 1 -

[0319] In formula (4-3), X 1 preferably contains a structure formed by removing two or more hydrogen atoms from any one of the structures represented by the following formulas (V-1) to (V-4). ​

[0320] [Chemical Formula 25]

[0321]

[0322] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group.

[0323] In formula (V-3), R X2 and R X3 each independently represent a hydrogen atom or a substituent, and R X2 and R X3 may bond to form a ring structure.

[0324] In formula (V-2), R X1 are each 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 still more preferably a methyl group or a trifluoromethyl group. The halogenated alkyl group is 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 Cl is preferred, and F is more preferred.

[0325] In formula (V-3), R X2 and R X3 are each independently preferably a hydrogen atom.

[0326] In the case where R X2 and R X3 bond to form a ring structure, the structure formed by the bonding of R X2 and R X3 is preferably a single bond, -O-, or -CR 2 -, more preferably -O- or -CR 2 -, and still 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 still more preferably a hydrogen atom.

[0327] When X 1 is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 is preferably a group represented by the following formula (V-1-1). In the following formula, * represents the bonding position of the four carbonyl groups bonded to X 1 in formula (4-3), and n1 represents an integer from 0 to 5, and is also preferably an integer from 1 to 5. Moreover, the hydrogen atoms in the following structure may be further substituted by known substituents such as a hydroxyl group and a hydrocarbon group. And when m in the above formula (4-3) is an integer from 1 to 4, it is preferred that m hydrogen atoms are substituted by R 1 in formula (4-3).

[0328] [Chemical Formula 26]

[0329]

[0330] At X 1 When it is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), X is preferably 1 a group represented by the following formula (V-2-1) or formula (V-2-2). From the viewpoint of reducing the amine value in the resin, etc., a group represented by formula (V-2-2) is preferred. In the following formulas, L X1 represents a single bond or -O-, and * represents the bonding position of the four carbonyl groups bonded to X in formula (4-3). And, R 1 is as defined above and the preferred mode is as above. And, the hydrogen atoms in these structures may be further substituted by known substituents such as a hydroxyl group and a hydrocarbon group. And, 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 X1 in formula (4-3). 1

[0331] [Chemical formula 27]

[0332]

[0333] At X 1 When it is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), X is preferably 1 a group represented by the following formula (V-3-1) or formula (V-3-2). From the viewpoint of reducing the dielectric constant, etc., a group represented by formula (V-3-2) is preferred. In the following formulas, * represents the bonding position of the four carbonyl groups bonded to X in formula (4-3). And, R 1 is as defined above and the preferred mode is as above. And, the hydrogen atoms in these structures may be further substituted by known substituents such as a hydroxyl group and a hydrocarbon group. And, 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 X2 and R X3 in formula (4-3). 1

[0334] [Chemical formula 28]

[0335]

[0336] At X 1 When it is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), X is preferably 1 a group represented by the following formula (V-4-1). In the following formula, * represents the bonding position of the four carbonyl groups bonded to X in formula (4-3). 1 ​​The bonding positions of the four carbonyl groups to be bonded, where n1 represents an integer from 0 to 5. Moreover, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups. And when m in the above formula (4-3) is an integer from 1 to 4, it is preferred that m hydrogen atoms are replaced by R in the formula (4-3) 1 substituted.

[0337] [Chemical formula 29]

[0338]

[0339] In addition, X 1 may be a group formed by removing m hydrogen atoms from the group represented by R in the above formula (4) 132 represented.

[0340] And X 1 preferably does not contain an imide structure in the structure.

[0341] In the present invention, the imide structure is the structure represented by -C(=O)N(-*)C(=O)-. * represents the bonding position to other structures.

[0342] And X 1 preferably does not contain a urethane bond, a urea bond, or an amide bond in the structure.

[0343] In the present invention, the urethane bond refers to the bond represented by *-O-C(=O)-NR N -*, where R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to a carbon atom respectively. R N is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.

[0344] In the present invention, the urea bond refers to the bond represented by *-NR N -C(=O)-NR N -*, where R N each independently represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to a carbon atom respectively. The preferred form of R N is as described above.

[0345] In the present invention, the amide bond is the bond represented by *-NR N -C(=O)-*, where R N represents a hydrogen atom or a monovalent organic group, and * represents the bonding position to a carbon atom respectively. The preferred form of R N is as described above.

[0346] In addition, X 1 is preferably free of an ester bond in the structure.

[0347] In the present invention, the ester bond is a bond represented by *-O-C(=O)-*.

[0348] wherein, X 1 preferably does not contain an imide structure, a urethane bond, a urea bond, and an amide bond, and preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, and an ester bond.

[0349] -Y 1 -

[0350] In formula (4-3), Y 1 is preferably a group containing a structure formed by removing two or more hydrogen atoms from any one of the structures represented by the above formulas (V-1) to (V-4).

[0351] In the case where Y 1 is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), preferably Y 1 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 bonding positions of the two nitrogen atoms bonded to Y in formula (4-3), and n1 represents an integer from 1 to 5. n of the hydrogen atoms in the following structure are replaced by R in formula (4-3). 1 The meaning of n is the same as the meaning of n in formula (4-3). And, the hydrogen atoms in the following structure may be further replaced by known substituents such as a hydroxyl group and a hydrocarbon group. 1

[0352] [Chemical formula 30]

[0353]

[0354] In the case where Y 1 is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), preferably Y 1 is a group represented by the following formula (V-2-3) or formula (V-2-4). From the viewpoint of reducing the dielectric constant, etc., it is preferably a group represented by formula (V-2-4). In the following formula, L X1 represents a single bond or -O-, * represents the bonding positions of the two nitrogen atoms bonded to Y in formula (4-3). And, the preferred mode of R 1 is as described above. n of the hydrogen atoms in the following structure are replaced by R in formula (4-3). X1 The meaning of n is the same as the meaning of n in formula (4-3). And, the hydrogen atoms in these structures may be further replaced by known substituents such as a hydroxyl group and a hydrocarbon group. 1

[0355] [Chemical formula 31]

[0356]

[0357] In Y 1 When it is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y is preferably 1 a group represented by the following formula (V-3-3) or formula (V-3-4). From the viewpoint of reducing the dielectric constant and the like, a group represented by formula (V-3-3) is preferred. In the following formulas, * represents the bonding positions of the two nitrogen atoms bonded to Y in formula (4-3). And, the preferred modes of R 1 and R X2 are as described above. n of the hydrogen atoms in the following structure is replaced by R X3 in formula (4-3). The meaning of n is the same as the meaning of n in formula (4-3). And, the hydrogen atoms in these structures may be further replaced by known substituents such as a hydroxyl group and a hydrocarbon group. 1

[0358] [Chemical formula 32]

[0359]

[0360] In Y 1 When it is a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y is preferably 1 a group represented by the following formula (V-4-2). In the following formula, * represents the bonding positions of the two nitrogen atoms bonded to Y in formula (4-3), and n1 represents an integer of 0 to 5. And, the mode where n1 is 0 is also one of the preferred modes of the present invention. n of the hydrogen atoms in the following structure is replaced by R 1 in formula (4-3). The meaning of n is the same as the meaning of n in formula (4-3). And, the hydrogen atoms in the following structure may be further replaced by known substituents such as a hydroxyl group and a hydrocarbon group. 1

[0361]

[0362] [Chemical formula 33]

[0363]

[0364] In addition, Y 1 may be a group formed by removing n hydrogen atoms from the group represented by R 131 in the above formula (4).

[0365] And, Y 1 preferably does not contain an imide structure in the structure.

[0365] And, Y 1 preferably does not contain a urethane bond, a urea bond, and an amide bond in the structure.

[0366] In addition, Y 1 preferably does not contain an ester bond in the structure.

[0367] Among them, Y 1 preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0368] Among them, X in formula (4-3) 1 and Y 1 each preferably contains a structure formed by removing two or more hydrogen atoms from any one of the structures represented by the above formulas (V-1) to (V-4).

[0369] In formula (4-3), m is preferably an integer of 0 to 2, more preferably 0 or 1. Moreover, the case where m is 0 is also one of the preferred embodiments of the present invention.

[0370] In formula (4-3), n is preferably 1 or 2, more preferably 2.

[0371] The polyimide also preferably has a fluorine atom in the structure. The content of the fluorine atom in the polyimide is preferably 10% by mass or more, more preferably 20% by mass or less.

[0372] For the purpose of improving the adhesion to the substrate, the polyimide can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be cited.

[0373] In order to improve the storage stability of the resin composition, it is preferable to cap the main chain terminals of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoactive ester compound, etc. Among them, it is more preferable to use a monoamine. As a preferable compound of the monoamine, 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-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, etc. can be cited. Two or more of these can be used, and a plurality of different terminal groups can also be introduced by reacting a plurality of capping agents.

[0374] -Imidization rate (ring closure rate)-

[0375] From the viewpoints of the film strength, insulation property, etc. of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

[0376] The upper limit of the above imidization rate is not particularly limited, and it may be 100% or less.

[0377] For example, the above imidization rate can be measured by the following method.

[0378] Measure the infrared absorption spectrum of the polyimide, and obtain the peak intensity P1 of the absorption peak derived from the imide structure, that is, the peak around 1377 cm -1 . Then, after heat-treating the polyimide at 350 °C for 1 hour, measure the infrared absorption spectrum again, and obtain the peak intensity P2 around 1377 cm -1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be obtained according to the following formula.

[0379] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0380] The polyimide may contain all of the repeating units of R 131 and R 132The combination is the same and the repeating unit represented by the above formula (4) may also contain R 131 and R 132 There are two or more kinds with different combinations and the repeating unit represented by the above formula (4). In addition to the repeating unit represented by the above formula (4), the polyimide may also contain other types of repeating units. As other types of repeating units, for example, the repeating unit represented by the following formula (2) can be cited.

[0381] The polyimide can be synthesized, for example, by the following methods: a method of reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a capping agent as a monoamine) at a low temperature; a method of reacting a tetracarboxylic dianhydride (partially substituted with a capping agent as an acid anhydride or a monoacyl chloride compound or a monoactive ester compound) with a diamine at a low temperature; a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (partially substituted with a capping agent as a monoamine) in the presence of a condensing agent; a method of obtaining a polyimide precursor by a method such as a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acylating the remaining dicarboxylic acid, and reacting it with a diamine (partially substituted with a capping agent as a monoamine), and using a known imidization reaction method to completely imidize it; or a method of stopping the imidization reaction halfway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer and the polyimide precursor. In addition, other known polyimide synthesis methods can also be applied.

[0382] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

[0383] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0384] The dispersity of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit value of the dispersity of the molecular weight of the polyimide is not particularly limited. For example, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0385] When the resin composition contains various polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above ranges. The weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the above various polyimides as one resin are also preferably within the above ranges.

[0386] [Manufacturing method of polyimide precursor, etc.]

[0387] For example, polyimide precursors and the like can be obtained by the following methods: a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine and a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine, etc. Among the above manufacturing methods, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferable.

[0388] Examples of the above condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc.

[0389] Examples of the above alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc.

[0390] Examples of the above halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, etc.

[0391] In the manufacturing method of polyimide precursors and the like, when carrying out the reaction, it is preferable to use an organic solvent. The organic solvent can be one kind or two or more kinds.

[0392] As the organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0393] In the manufacturing method of polyimide precursors and the like, when carrying out the reaction, it is preferable to add a basic compound. The basic compound can be one kind or two or more kinds.

[0394] The basic compound can be appropriately determined according to the raw materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, and the like.

[0395] -End-capping agent-

[0396] In the production method of a polyimide precursor or the like, in order to further improve the storage stability, it is preferable to block the carboxylic anhydride, acid anhydride derivative or amino group remaining at the resin terminal of the polyimide precursor or the like. When blocking the carboxylic anhydride and acid anhydride derivative remaining at the resin terminal, as the end-capping agent, monoalcohol, phenol, thiol, benzenethiol, monoamine, etc. can be cited. Considering the reactivity and the stability of the film, it is more preferable to use monoalcohol, phenols, and monoamine. As the preferred compounds of monoalcohol, primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc., secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc., and tertiary alcohols such as tert-butanol, adamantanol, etc. can be cited. As the preferred compounds of phenols, phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, hydroxystyrene, etc. can be cited. And, as the preferred compounds of monoamine, 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-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, etc. These can be used in two or more kinds, or a plurality of different end groups can be introduced by reacting a plurality of end-capping agents.

[0397] Moreover, when blocking the amino group at the end of the blocking resin, it can be blocked with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for the amino group are preferably carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic carboxylic anhydrides, etc., and more preferably carboxylic anhydrides and carboxylic acid chlorides. Preferred compounds as carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. And, preferred compounds as carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, benzoyl chloride, etc.

[0398] -Solid precipitation-

[0399] In the manufacturing method of polyimide precursors, etc., it may include a step of precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is put into a poor solvent such as water, lower aliphatic alcohols or a mixed solution thereof, and the polymer component is precipitated, whereby it is precipitated as a solid and dried to obtain a polyimide precursor, etc. In order to improve the purification degree, operations such as re-dissolution, re-precipitation, and drying can be repeatedly performed on the polyimide precursor, etc. In addition, it may also include a step of removing ionic impurities using an ion exchange resin.

[0400] 〔Content〕

[0401] 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 even more preferably 50% by mass or more, relative to the total solid content of the resin composition. And, 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, even more preferably 97% by mass or less, and still more preferably 95% by mass or less, relative to the total solid content of the resin composition.

[0402] The resin composition of the present invention may contain only one kind of specific resin, or may contain two or more kinds of specific resins. When containing two or more kinds, the total amount is preferably within the above range.

[0403] The resin composition of the present invention also preferably contains at least two kinds of resins.

[0404] Specifically, the resin composition of the present invention may contain two or more kinds in total of the specific resin and other resins described later, or may contain two or more kinds of specific resins, and preferably contains two or more kinds of specific resins.

[0405] When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains two or more polyimide precursors having different structures derived from dianhydrides (R in the above formula (2)) 115 ).

[0406] <Other resins>

[0407] 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").

[0408] Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, polyester resins, and the like.

[0409] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[0410] For example, by adding a (meth)acrylic resin to the resin composition in place of the polymerizable compound described later or adding a (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. The weight average molecular weight of the (meth)acrylic resin is 20,000 or less and the polymerizable group value is high (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1×10 -3 mol / g or more).

[0411] 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, still further preferably 5% by mass or more, and even further preferably 10% by mass or more, based on the total solid content of the resin composition.

[0412] The content of the 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, still further preferably 60% by mass or less, and even further preferably 50% by mass or less, based on the total solid content of the resin composition.

[0413] As a preferred embodiment of the resin composition of the present invention, it can also be set to a mode in which the content of other resins is low. In the above mode, 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, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, relative to the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0414] The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds of other resins. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0415] <Compound B>

[0416] [Compound B1]

[0417] The first resin composition of the present invention contains Compound B1.

[0418] Compound B1 is a compound represented by the following formula (1-1) and having an ethylenic unsaturated bond valence of 3.0 mmol / g or more.

[0419] [Chemical formula 34]

[0420]

[0421] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar 1 each independently represents an aromatic group which may have a substituent, Z represents a hydrogen atom or an n-valent organic group, and Z does not contain -X 1 -C(=O)-C(=O)-X 2 - such a structure, X 1 and X 2 each independently represents -O- or -NH-, n represents an integer of 1 to 6, m represents 1 or 2. When n is 1, m is 2 and Z is a hydrogen atom. When n is an integer of 2 to 6, Z represents an n-valent organic group, and Z and Ar 1 do not have an ethylenic unsaturated bond structure.

[0422] [Ethylenic unsaturated bond valence]

[0423] The ethylenic unsaturated bond valence in Compound B1 (the content of ethylenic unsaturated bonds relative to 1 g of Compound B1) is 3.0 mmol / g or more, preferably 3.3 mmol / g or more, more preferably 3.5 mmol / g or more, and further preferably 4.0 mmol / g or more.

[0424] The upper limit of the valence of the ethylenically unsaturated bond is not particularly limited and can be set, for example, to 20.0 mmol / g or less.

[0425] [Formula (1-1)]

[0426] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0427] Here, R in formula (1-1) 1 is a hydrogen atom and Ar 1 is an aromatic hydrocarbon group which may have a substituent, and this is also one of the preferred embodiments of the present invention. In the above embodiment, Ar 1 is preferably a group formed by removing m + 1 hydrogen atoms from a benzene ring and may have a substituent.

[0428] In formula (1-1), Ar 1 each independently represents an aromatic group which may have a substituent.

[0429] As the above aromatic group, it may be an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, but preferably an aromatic hydrocarbon group which may have a substituent, more preferably a group formed by removing m + 1 hydrogen atoms from a benzene ring and may have a substituent.

[0430] The heteroatom in the above aromatic heterocyclic group is not particularly limited, but examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, etc.

[0431] As the above aromatic heterocyclic group, examples thereof include 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 triazine ring, etc.

[0432] The substituent in the above aromatic group is not particularly limited, but examples thereof include an alkyl group, an aromatic group, a halogen atom, etc.

[0433] Moreover, the embodiment in which the above aromatic group does not have m structures in formula (1-1) and substituents other than Z is also one of the preferred embodiments of the present invention.

[0434] In formula (1-1), Z represents a hydrogen atom or an n-valent organic group, and Z does not contain -X 1 -C(=O)-C(=O)-X 2 - such a structure, X 1 and X 2Independently represent -O- or -NH- respectively. When n is 1, m is 2 and Z is a hydrogen atom. When n is an integer from 2 to 6, Z represents an n-valent organic group.

[0435] In formula (1-1), when n is an integer from 2 to 6, Z is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, -O-, -C(=O)-, an imino group, or a group represented by two or more bonds thereof.

[0436] Here, when n is an integer from 4 to 6, Z is preferably a saturated aliphatic hydrocarbon group, or a group represented by a bond of a saturated aliphatic hydrocarbon group and -O-, -C(=O)- and an imino group.

[0437] Moreover, in formula (1-1), Z is preferably a group represented by the following formula (Z-1) or formula (Z-2).

[0438] [Chemical formula 35]

[0439]

[0440] In formula (Z-1), L Z1 represents an n-valent organic group, and L Z2 independently represent a single bond or a hydrocarbon group respectively. The meaning of n is the same as that of n in formula (1-1), and * represents the bonding position with Ar 1 in formula (1-1).

[0441] In formula (Z-2), L Z3 represents an a-valent organic group, and L Z4 independently represent a single bond or a hydrocarbon group respectively. The meaning of 2×a is the same as that of n in formula (1-1), and * represents the bonding position with Ar 1 in formula (1-1).

[0442] In formula (Z-1), L Z1 is preferably a structure represented by any one of the following formulas (L-1) to (L-4).

[0443] From the viewpoint of chemical resistance, L Z1 is preferably a structure represented by the following formula (L-1).

[0444] From the viewpoint of elongation at break, L Z1 is preferably a structure represented by the following formula (L-2).

[0445] [Chemical formula 36]

[0446]

[0447] In formula (L-1), Ar 1 and Ar2 Each independently represents a phenylene group in which a hydrogen atom may be substituted with a substituent, R L1 and R L2 Each independently represents a hydrocarbon group which may have a substituent, R L1 and R L2 may be bonded to form a ring structure, and # represents the bonding position to the oxygen atom in formula (Z-1). In the case where L Z1 is a group represented by formula (L-1), n in formula (Z-1) and formula (1-1) is 2. As the substituents in the above Ar 1 and Ar 2 , known substituents can be used within the range where the effects of the present invention can be obtained. For example, halogen atoms, hydrocarbon groups such as alkyl groups, alkoxy groups, aryloxy groups, etc. can be cited.

[0448] In formula (L-2), L L1 and L L2 Each independently represents a hydrocarbon group, n1 represents an integer of 0 or more, and # represents the bonding position to the oxygen atom in formula (Z-1). In the case where L Z1 is a group represented by formula (L-2), n in formula (Z-1) and formula (1-1) is 2.

[0449] In formula (L-3), L L3 Each independently represents a single bond or a divalent linking group, and # represents the bonding position to the oxygen atom in formula (Z-1). In the case where L Z1 is a group represented by formula (L-3), n in formula (Z-1) and formula (1-1) is 3.

[0450] In formula (L-4), Ar 3 and Ar 4 Each independently represents a phenylene group in which a hydrogen atom may be substituted with a substituent, and # represents the bonding position to the oxygen atom in formula (Z-1). In the case where L Z1 is a group represented by formula (L-4), n in formula (Z-1) and formula (1-1) is 2. As the substituents in the above Ar 3 and Ar 4 , known substituents can be used within the range where the effects of the present invention can be obtained. For example, halogen atoms, hydrocarbon groups such as alkyl groups, alkoxy groups, aryloxy groups, etc. can be cited.

[0451] In formula (L-1), R L1 and R L2 Each independently is preferably a methyl group or a trifluoromethyl group.

[0452] In formula (L-1), Ar 1 and Ar 2 Are both preferably 1,4-phenylene.

[0453] In formula (L-1), as R L1 bonded to R L2 The ring structure formed by bonding can include a fluorene ring structure, a cyclohexane ring structure, etc. According to this method, a resin composition with excellent resolution can be obtained.

[0454] In formula (L-2), L L1 and L L2 are each independently preferably an alkylene group, more preferably an alkylene group having 2 to 20 carbon atoms, and still more preferably an alkylene group having 2 to 10 carbon atoms.

[0455] In formula (L-2), n1 is preferably an integer from 0 to 8, more preferably an integer from 0 to 4.

[0456] Moreover, in formula (L-2), the minimum value of the number of atoms connecting two # (connection chain length) is preferably 2 to 20, more preferably 4 to 20, and still more preferably 8 to 20.

[0457] The "minimum value of the number of atoms connecting two # (connection chain length)" means the shortest (minimum number of atoms) atomic chain on the path between the two #s to be connected as the connection objects.

[0458] In formula (L-3), L L3 are each independently preferably a single bond or a hydrocarbon group, more preferably a single bond or an alkylene group, and still more preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

[0459] In formula (L-4), Ar 3 and Ar 4 are both preferably 1,4-phenylene.

[0460] In formula (Z-1), L Z2 is preferably a single bond or an alkylene group, more preferably a single bond or a methylene group.

[0461] In formula (Z-2), L Z3 is preferably an a-valent saturated aliphatic hydrocarbon group, more preferably an a-valent saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and still more preferably an a-valent saturated aliphatic hydrocarbon group having 2 to 12 carbon atoms.

[0462] In formula (Z-2), L Z4 are each independently preferably a single bond or an alkylene group, more preferably an alkylene group, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.

[0463] In formula (1-1), when n is an integer from 2 to 6, as Z, the following structures can be cited, but are not limited thereto. In the following formula, * represents the bonding position with Ar in formula (1-1) 1 bonding position.

[0464] [Chemical Formula 37]

[0465]

[0466] In formula (1-1), n is preferably an integer of 2 to 4. Further, from the viewpoint of elongation at break, the case where n is 2 is also one of the preferred embodiments of the present invention. In addition, from the viewpoint of chemical resistance, the cases where n is 3 or 4 are also one of the preferred embodiments of the present invention.

[0467] In formula (1-1), the case where m is 1 is also one of the preferred embodiments of the present invention.

[0468] The first resin composition preferably contains two or more kinds of compound B1, or contains compound B1 and a polymerizable compound different from compound B1.

[0469] As the polymerizable compound different from compound B1, the polymerizable compounds described later can be mentioned.

[0470] For example, from the viewpoint of elongation at break, it is preferable to use a radical crosslinking agent described later and a compound having one or two radical polymerizable groups.

[0471] For example, from the viewpoint of chemical resistance, it is preferable to use a radical crosslinking agent described later and a compound having three or more radical polymerizable groups.

[0472] The molecular weight of compound B1 is preferably 2,000 or less, more preferably 1,000 or less, and further preferably 750 or less.

[0473] The lower limit of the above molecular weight is not particularly limited. For example, it is preferably 130 or more, more preferably 150 or more, and further preferably 200 or more.

[0474] [Compound B2]

[0475] The second resin composition of the present invention contains compound B2 represented by the following formula (1-2).

[0476] [Chemical Formula 38]

[0477]

[0478] In formula (1-2), L 1 ~L 3 each independently represents a divalent linking group having no aromatic ring structure, and R a each independently represents a hydrogen atom or a monovalent organic group.

[0479] In formula (1-2), L 1 ~L 3Each is independently preferably an aliphatic hydrocarbon group or a group represented by a bond of an aliphatic hydrocarbon group and at least one structure selected from -O-, -C(=O)-, and an imino group.

[0480] Here, L 1 ~L 3 Each is independently also preferably a group represented by the following formula (L-5).

[0481] [Chemical formula 39]

[0482] #-L L5 -O-L L6 -*(L-5)

[0483] In formula (L-5), L L5 and L L6 each independently represents a single bond or an alkylene group, # represents the bonding position to the nitrogen atom in formula (1-2), and * represents the bonding position to the benzene ring in formula (1-2).

[0484] In formula (L-5), L L5 and L L6 are each independently preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

[0485] Here, L L5 and L L6 both being single bonds and the case where L L5 is methylene and L L6 is ethylene are also one of the preferred modes of the present invention.

[0486] The second resin composition preferably contains two or more kinds of compound B2, or contains compound B2 and a polymerizable compound different from compound B2.

[0487] As the polymerizable compound different from compound B2, the polymerizable compounds described below can be mentioned.

[0488] For example, from the viewpoint of elongation at break, it is preferable to use a radical crosslinking agent described below and a compound having one or two radical polymerizable groups.

[0489] For example, from the viewpoint of chemical resistance, it is preferable to use a radical crosslinking agent described below and a compound having three or more radical polymerizable groups.

[0490] The molecular weight of compound B2 is preferably 2,000 or less, more preferably 1,000 or less, and still more preferably 800 or less.

[0491] The lower limit of the above molecular weight is not particularly limited, and for example, it is preferably 480 or more.

[0492] [Synthesis method]

[0493] Compound B can be synthesized, for example, by the method described in the following examples. Alternatively, it can also be synthesized by other known synthesis methods, and the synthesis method is not particularly limited.

[0494] 〔Specific examples〕

[0495] Specific examples of Compound B are not particularly limited, but B-1 to B-19 used in the examples can be cited.

[0496] 〔Content〕

[0497] The content of Compound B relative to the total solid content of the resin composition of the present invention is preferably 1.0 to 30% by mass. The lower limit is more preferably 2.0% by mass or more, further preferably 3.0% by mass or more, and particularly preferably 4.0% by mass or more. The upper limit is more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0498] Compound B can be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

[0499] Moreover, when the resin composition contains Compound B and a polymerizable compound different from Compound B, the content of Compound B relative to the total amount of these is preferably 20 to 95% by mass. The lower limit is more preferably 30% by mass or more, further preferably 35% by mass or more, and particularly preferably 40% by mass or more. The upper limit is more preferably 90% by mass or less, further preferably 85% by mass or less, and particularly preferably 80% by mass or less.

[0500] <Polymerizable compound>

[0501] The resin composition of the present invention preferably contains a polymerizable compound.

[0502] The compound corresponding to the above Compound B does not correspond to the polymerizable compound mentioned here.

[0503] Examples of the polymerizable compound include a radical crosslinking agent or other crosslinking agents.

[0504] 〔Radical crosslinking agent〕

[0505] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0506] The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenic unsaturated bond is preferably included. Examples of the group containing an ethylenic unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc.

[0507] Among them, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, (meth)acryloyl group is more preferred.

[0508] 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.

[0509] As the compound having two or more of the above-mentioned 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.

[0510] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention also preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0511] 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.

[0512] As specific examples of the radical crosslinking agent, there can be mentioned unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides. Preferred are esters of unsaturated carboxylic acids with polyol compounds and amides of unsaturated carboxylic acids with polyamine compounds. Also, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, and mercapto group with monofunctional or polyfunctional isocyanate compounds or epoxy compounds, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can be preferably used. And addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines, and thiols are preferred. Further, substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen group and tosyl group with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. And as another example, instead of the above-mentioned unsaturated carboxylic acids, a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinylbenzene, and allyl ether can be used. As specific examples, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, and these contents are incorporated into this specification.

[0513] 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 the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0514] As other preferred radical crosslinking agents, examples include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0515] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0516] Examples of commercially available products as free radical crosslinking agents include tetrafunctional acrylate SR-494 having four ethenyloxy chains, difunctional methacrylate SR-209, 231, 239 (the above are manufactured by Sartomer Company, Inc.) having four ethenyloxy chains, hexafunctional acrylate DPCA-60 having six pentenyloxy chains, trifunctional acrylate TPA-330 having three isobutenyloxy chains (the above are manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10, UAB-140 (the above are manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (the above are manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (the above are manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0517] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication No. Sho 48-041708, Japanese Unexamined Patent Publication No. Sho 51-037193, Japanese Examined Patent Publication No. Hei 02-032293, Japanese Examined Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Hei 62-039417, Japanese Patent Publication No. Hei 62-039418 are also preferred. As free radical crosslinking agents, compounds having an amino structure and a thioether structure in the molecule described in Japanese Unexamined Patent Publication No. Sho 63-277653, Japanese Unexamined Patent Publication No. Sho 63-260909, Japanese Unexamined Patent Publication No. Hei 01-105238 can also be used.

[0518] The free radical crosslinking agent may be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphoric acid groups. 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 anhydride. Particularly preferred are the following compounds: among the free radical crosslinking agents having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510, M-520, etc. manufactured by TOAGOSEI CO., LTD. can be cited.

[0519] The acid value of the free radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in production is excellent and the developability is excellent. Moreover, the polymerizability is good. The above acid value is measured according to the description in JIS K 0070:1992.

[0520] As the free radical crosslinking agent, a free radical crosslinking agent having at least one of a urethane bond and a carbamate bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.

[0521] In the present invention, the urethane bond means a bond represented by *-NR N -C(=O)-NR N -*, where R N each independently represents a hydrogen atom or a monovalent organic group, and * respectively represents the bonding position to a carbon atom.

[0522] In the present invention, the carbamate bond means a bond represented by *-O-C(=O)-NR N -*, where R N represents a hydrogen atom or a monovalent organic group, and * respectively represents the bonding position to a carbon atom.

[0523] When the resin composition contains the crosslinking agent U, the chemical resistance, resolution, etc. may sometimes be improved.

[0524] The mechanism by which the above effects can be obtained is not yet clear, but it is considered that, for example, when curing is carried out by heating or the like, a part of the crosslinking agent U thermally decomposes, thereby generating amines and the like, and the amines and the like promote the cyclization of the precursor of the cyclic resin such as the polyimide precursor.

[0525] The crosslinking agent U may have only one urethane bond or carbamate bond, may have one or more urethane bonds and one or more carbamate bonds, may have two or more urethane bonds and no carbamate bond, or may have two or more carbamate bonds and no urethane bond.

[0526] The total number of urea bonds and urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 or 2.

[0527] When crosslinking agent U does not have a urethane bond, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 or 2.

[0528] In the case where crosslinking agent U does not have a urea bond, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 or 2.

[0529] The radically polymerizable group in crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, etc. A (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group or a maleimide group is preferred, and a (meth)acryloyloxy group is more preferred.

[0530] When crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.

[0531] The number of radically polymerizable groups in crosslinking agent U may be only 1 or two or more, preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4.

[0532] The value of the radically polymerizable group in crosslinking agent U (the mass of the compound per 1 mol of the radically polymerizable group) is preferably 150 to 400 g / mol.

[0533] From the viewpoint of the chemical resistance of the cured product, the lower limit of the above-mentioned radically polymerizable group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, still further preferably 220 g / mol or more, still further preferably 230 g / mol or more, still further preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0534] From the viewpoint of developability, the upper limit of the above-mentioned radically polymerizable group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0535] Among them, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0536] Crosslinking agent U preferably has, for example, a structure represented by the following formula (U-1).

[0537] [Chemical Formula 40]

[0538]

[0539] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an (n + 1)-valent organic group, X is a radically polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0540] R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.

[0541] R N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.

[0542] Z U1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a group formed by bonding a hydrocarbon group with at least one group selected from -O-, -C(=O)-, -S-, -S(=O) 2 - and -NR N -.

[0543] As the above hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is further preferred. Examples of the above hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these. R N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a methyl group.

[0544] Z U2 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a group formed by bonding a hydrocarbon group with at least one group selected from -O-, -C(=O)-, -S-, -S(=O) 1 - and -NR N -.

[0545] As the above hydrocarbon group, examples include those similar to those in Z U1The hydrocarbon groups exemplified herein are the same, and the preferred modes are also the same.

[0546] X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, etc. A (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group or a maleimide group is preferred, and a (meth)acryloyloxy group is more preferred.

[0547] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, and particularly preferably 1.

[0548] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2.

[0549] The crosslinking agent U also preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group.

[0550] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, and an alcoholic hydroxyl group is preferred.

[0551] From the viewpoint of the chemical resistance of the obtained cured film, as the alkyleneoxy group, an alkyleneoxy group having 2 to 20 carbon atoms is preferred, an alkyleneoxy group having 2 to 10 carbon atoms is more preferred, an alkyleneoxy group having 2 to 4 carbon atoms is still more preferred, an ethylene group or a propylene group is further more preferred, and an ethylene group is particularly preferred.

[0552] The alkyleneoxy group may be included in the crosslinking agent U as a polyalkyleneoxy group. In this case, the repeating number of the alkyleneoxy group is preferably 2 to 10, more preferably 2 to 6.

[0553] The amide group means a bond represented by -C(=O)-NR N -. R N is as described above. When the crosslinking agent U has an amide group, the crosslinking agent U can contain, for example, an amide group as a group represented by R-C(=O)-NR N -* or a group represented by *-C(=O)-NR N -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0554] The crosslinking agent U may have two or more structures selected from a hydroxyl group, an alkyleneoxy group (wherein, when forming a polyalkyleneoxy group, it is a polyalkyleneoxy group), an amide group and a cyano group in the molecule, but a mode in which only one is present in the molecule is also preferred.

[0555] The above-mentioned hydroxyl group, alkoxy group, amide group and cyano group can be present at any position of the crosslinking agent U. However, from the viewpoint of chemical resistance, regarding the crosslinking agent U, it is also preferred that at least one selected from the above-mentioned hydroxyl group, alkoxy group, amide group and cyano group is connected to at least one radically polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").

[0556] In particular, when the crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in the crosslinking agent U is connected to at least one selected from a hydroxyl group, an alkoxy group, an amide group and a cyano group via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-2").

[0557] When the crosslinking agent U contains an alkoxy group (wherein when forming a polyalkoxy group, it is a polyalkoxy group) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the alkoxy group (wherein when forming a polyalkoxy group, it is a polyalkoxy group) is not particularly limited, and a hydrocarbon group, a radically polymerizable group or a group represented by a combination thereof is preferred. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferred, a hydrocarbon group having 18 or less carbon atoms is more preferred, and a hydrocarbon group having 16 or less carbon atoms is further preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by a bond thereof can be mentioned. And, the preferred mode of the radically polymerizable group is the same as the preferred mode of the radically polymerizable group in the above-mentioned crosslinking agent U.

[0558] When the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, and a hydrocarbon group, a radically polymerizable group or a group represented by a combination thereof is preferred. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferred, a hydrocarbon group having 18 or less carbon atoms is more preferred, and a hydrocarbon group having 16 or less carbon atoms is further preferred. And, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by a bonding thereof can be mentioned. The preferred mode of the radically polymerizable group is the same as the preferred mode of the radically polymerizable group in the above-mentioned crosslinking agent U. And, in the above mode, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2.

[0559] Among them, from the viewpoints of adhesion to the substrate, chemical resistance and suppression of Cu voids, the crosslinking agent U preferably has a hydroxyl group.

[0560] From the viewpoints such as compatibility with a specific resin, the crosslinking agent U preferably contains an aromatic group.

[0561] The above aromatic group is preferably directly bonded to a urethane bond or a carbamate bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urethane bonds or carbamate bonds, one of the urethane bonds or carbamate bonds is preferably directly bonded to the aromatic group.

[0562] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or a structure in which they form a condensed ring, and is preferably an aromatic hydrocarbon group.

[0563] As the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred, and a group formed by removing two or more hydrogen atoms from a benzene ring structure is further preferred.

[0564] As the above aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further condensed with other rings, such as indole and benzimidazole.

[0565] As the heteroatom contained in the above aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[0566] The above aromatic group is preferably contained in, for example, a linking group that connects two or more radically polymerizable groups and contains a urethane bond or a carbamate bond, or a linking group that connects at least one selected from the above hydroxyl group, alkoxy group, amide group and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.

[0567] The number of atoms (linking chain length) between the urethane bond or carbamate bond and the radically polymerizable group in the crosslinking agent U is not particularly limited, preferably 30 or less, more preferably 2 to 20, and further preferably 2 to 10.

[0568] When the crosslinking agent U contains a total of two or more urethane bonds or carbamate bonds, when it contains two or more radically polymerizable groups, or when it contains two or more urethane bonds or carbamate bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urethane bond or carbamate bond and the radically polymerizable group may be within the above range.

[0569] In this specification, the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group" refers to the shortest (minimum number of atoms) atomic chain in the atomic chain on the path connecting two atoms or atomic groups to be linked. For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy) is 2.

[0570] [Chemical formula 41]

[0571]

[0572] 〔Axis of symmetry〕

[0573] The crosslinking agent U is also preferably a compound having a structure without an axis of symmetry.

[0574] The crosslinking agent U not having an axis of symmetry means that it is a left - right asymmetric compound and does not have an axis that generates a molecule identical to the original molecule by rotating the whole compound. Moreover, when marking the structural formula of the crosslinking agent U on the paper surface, the crosslinking agent U not having an axis of symmetry means that the structural formula of the crosslinking agent U cannot be marked in a form having an axis of symmetry.

[0575] It is considered that since the crosslinking agent U does not have an axis of symmetry, the aggregation between the crosslinking agents U in the composition film is suppressed.

[0576] 〔Molecular weight〕

[0577] The molecular weight of the crosslinking agent U is preferably 100 - 2,000, more preferably 150 - 1500, and even more preferably 200 - 900.

[0578] The production method of the crosslinking agent U is not particularly limited. For example, it can be obtained by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group or an amino group.

[0579] The following shows specific examples of the crosslinking agent U, but the crosslinking agent U is not limited thereto.

[0580] [Chemical formula 42]

[0581]

[0582] [Chemical formula 43]

[0583]

[0584] [Chemical formula 44]

[0585]

[0586] From the viewpoints of the resolution of the pattern and the stretchability of the film, a 2-functional methacrylate or acrylate is preferably used as the resin composition.

[0587] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, EO-modified dimethacrylate of isocyanuric acid, other 2-functional acrylates having a urethane bond, 2-functional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed.

[0588] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a molecular weight of the polyethylene glycol chain of about 200.

[0589] From the viewpoint of suppressing the warpage of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As the monofunctional radical crosslinking agent, in order to suppress the volatilization before exposure, a compound having a boiling point of 100 ° C or higher under normal pressure is also preferably used.

[0590] In addition, as the radical crosslinking agent having two or more functions, allyl compounds such as diallyl phthalate and triallyl trimellitate can be cited.

[0591] In the case of containing a radical crosslinking agent, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0592] The radical crosslinking agent may be used alone as one kind, or two or more kinds may be used in combination. In the case of using two or more kinds in combination, the total amount thereof is preferably within the above range.

[0593] 〔Other crosslinking agents〕

[0594] The resin composition of the present invention preferably contains other crosslinking agents different from the above radical crosslinking agents.

[0595] Examples of the other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated into this specification.

[0596] 〔Polymerization initiator〕

[0597] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and particularly preferably contains a photopolymerization initiator.

[0598] The photopolymerization initiator is preferably a photo radical polymerization initiator. There is no particular limitation on the photo radical polymerization initiator, and it can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it may also be an active agent that acts with a photosensitizer excited by light to generate active radicals.

[0599] The photo radical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of about 50 L·mol -1 ·cm -1 in the range of about 240 to 800 nm (preferably 330 to 500 nm) in wavelength. The molar extinction coefficient of the 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 ethyl acetate solvent at a concentration of 0.01 g / L.

[0600] As the photo radical polymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (such as compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminophenylethanones, α-hydroxy ketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron-arene complexes, etc. Regarding the detailed content of these, reference can be made to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and this content is incorporated into this specification. Also, compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, Japanese Patent No. 6301489, peroxide-based photoinitiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photoinitiators described in International Publication No. 2018 / 221177, photoinitiators described in International Publication No. 2018 / 110179, photoinitiators described in Japanese Patent Application Laid-Open No. 2019-043864, photoinitiators described in Japanese Patent Application Laid-Open No. 2019-044030, peroxide-based initiators described in Japanese Patent Application Laid-Open No. 2019-167313, and these contents are incorporated into this specification.

[0601] As the ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and this content is incorporated into this specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0602] In one embodiment of the present invention, as the photo radical polymerization initiator, hydroxyacetophenone compounds, aminophenylethanone compounds, and acylphosphine compounds can be preferably used. More specifically, for example, aminophenylethanone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated into this specification.

[0603] As the α-hydroxy ketone-based initiator, it is possible to use Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (the above are manufactured by BASF).

[0604] As the α-amino ketone-based initiator, it is possible to use Omnirad 907, Omnirad 369, Omnirad369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (the above are manufactured by BASF).

[0605] As the aminoacetophenone-based initiator, acylphosphine oxide-based initiator, metallocene compound, for example, it is also possible to preferably use the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0606] As the photo radical polymerization initiator, oxime compounds can be more preferably cited. By using oxime compounds, it is possible to further effectively improve the exposure latitude. The exposure latitude (exposure margin) of oxime compounds is wide, and they also act as photo-curing accelerators, so they are particularly preferred.

[0607] As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pages 1653-1660), compounds described in J.C.S. Perkin II (1979, pages 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pages 202-232), compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc. are cited, and this content is incorporated into the present specification.

[0608] As preferred oxime compounds, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(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, etc. are cited. In the resin composition, it is particularly preferred to use an oxime compound as a photo radical polymerization initiator. The oxime compound as a photo radical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0609] [Chemical formula 45]

[0610]

[0611] As commercially available products of oxime compounds, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photo radical polymerization initiator 2 described in Japanese Unexamined Patent Application Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronl y 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), SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be cited. Further, oxime compounds having the following structures can also be used.

[0612] [Chemical formula 46]

[0613]

[0614] As the photo radical polymerization initiator, for example, oxime compounds having a fluorene ring, oxime compounds in which at least one benzene ring having a carbazole ring has a naphthalene ring skeleton, and oxime compounds having a fluorine atom described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189 can also be used.

[0615] Further, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These are incorporated into this specification.

[0616] As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar formed by introducing an electron-withdrawing group into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. As the above aromatic ring group Ar 0X1 0X1Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred from the viewpoint of easily forming a film having excellent light resistance. A benzoyl group is further preferred. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylthio group, an arylthio group, an acyl group, and an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and an amino group are more preferred. An alkoxy group, an alkylthio group, and an amino group are further preferred.

[0617] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compounds represented by formula (OX2).

[0618] [Chemical formula 47]

[0619]

[0620] 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 heterocyclic oxy group, an alkylthio group, an arylthio 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,

[0621] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group,

[0622] R X3 ~R X14 each independently represents a hydrogen atom or a substituent.

[0623] However, at least one of R X10 ~R X14 is an electron-withdrawing group.

[0624] In the above formula, it is preferred that R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 are hydrogen atoms.

[0625] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the content of which is incorporated herein by reference.

[0626] As particularly preferred oxime compounds, mention may be made of oxime compounds having specific substituents shown in JP-A-2007-269779, oxime compounds having a thioaryl group shown in JP-A-2009-191061, etc., and the content is incorporated into this specification.

[0627] From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably selected from trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone 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, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds.

[0628] Moreover, the photo radical polymerization initiator is a trihalomethyltriazine 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, an acetophenone compound, and more preferably at least one compound selected from trihalomethyltriazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, benzophenone compounds, and still more preferably a metallocene compound or an oxime compound.

[0629] As the photo radical polymerization initiator, it is also possible to use the compounds described in paragraphs 0175 to 0179 described in WO 2021 / 020359, the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469, and the content is incorporated into this specification.

[0630] As the photo radical polymerization initiator, a bifunctional or polyfunctional photo radical polymerization initiator having three or more functional groups can be used. By using such a photo radical polymerization initiator, two or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. Further, in the case where an asymmetric structure compound is used, the crystallinity decreases and the solubility in a solvent or the like increases, and precipitation is less likely to occur with the passage of time, whereby the stability over time of the resin composition can be improved. Specific examples of the bifunctional or polyfunctional photo radical polymerization initiator having three or more functional groups include the dimer of the oxime compound described in paragraphs 0407 to 0412 of Japanese Patent Application Laid-Open No. 2010-527339, Japanese Patent Application Laid-Open No. 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of Japanese Patent Application Laid-Open No. 2016-532675, the dimer of the oxime compound described in paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, compound (E) and compound (G) described in Japanese Patent Application Laid-Open No. 2013-522445, Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Application Laid-Open No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Application Laid-Open No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc. The content is incorporated into this specification.

[0631] 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, still more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0632] In addition, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator, and thus the crosslinking based on the photopolymerization initiator may be further promoted by heating with an oven, a hot plate or the like.

[0633] [Sensitizer]

[0634] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator or the like, and causes effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo chemical changes and decompose, and radicals, acids or bases are generated.

[0635] As sensitizers that can be used, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazolyl azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, etc. can be used.

[0636] As sensitizers, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)isoindolothiazole, 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 (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, dibenzylacetamide, benzoylaniline, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. can be cited.

[0637] Also, other sensitizing dyes can be used.

[0638] Regarding the detailed content of the sensitizing dyes, reference can be made to the description in paragraphs 0161 to 0163 of Japanese Patent Laid-Open No. 2016-027357, and this content is incorporated herein.

[0639] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0640] [Chain transfer agent]

[0641] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds having a thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. These can supply hydrogen to a low-reactivity radical to generate a radical, or generate a radical by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

[0642] In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used as the chain transfer agent, and the content is incorporated into this specification.

[0643] 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 still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that their total is within the above range.

[0644] In addition, the polymerization initiator is preferably a photoacid generator. As the photoacid generator, a photoacid generator that generates radicals is preferred.

[0645] Specifically, a compound that absorbs light, decomposes to generate radicals, and extracts hydrogen from a solvent or the acid generator itself, etc., to generate an acid is preferred.

[0646] Examples of the photoacid generator include quinone diazide compounds, oxime sulfonate compounds, organic halogen compounds, organic boric acid chloride compounds, disulfone compounds, onium salts, etc., and onium salts are preferred.

[0647] Examples of the onium salt include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts and the like.

[0648] The onium salt is a salt of a cation having an onium structure and an anion, and the above-mentioned cation and anion may be bonded via a covalent bond or may not be bonded via a covalent bond.

[0649] That is, the onium salt may be an inner salt having a cationic part and an anionic part in the same molecular structure, or may be an intermolecular salt in which a cation molecule and an anion molecule of different molecules are ionically bonded, but an intermolecular salt is preferred. In the composition of the present invention, the above-mentioned cationic part or cation molecule and the above-mentioned anionic part or anion molecule may be bonded by an ionic bond or may be dissociated.

[0650] [Sulfonium salt]

[0651] In the present invention, the sulfonium salt represents a salt of a sulfonium cation and an anion.

[0652]

[0653] As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triaryl sulfonium cation is more preferred.

[0654] Moreover, as the sulfonium cation, a cation represented by the following formula (103) is preferred.

[0655] [Chemical formula 48]

[0656]

[0657] In formula (103), R 8 ~R 10 each independently represents a hydrocarbon group.

[0658] R 8 ~R 10 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and still further preferably a phenyl group.

[0659] R 8 ~R 10 may have a substituent. Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and the like. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred.

[0660] R 8 ~R 10 ​They may be the same group or different groups. From the viewpoint of synthesis suitability, they are preferably the same group.

[0661] - Anion -

[0662] There is no particular limitation on the anion, and it may be selected considering the acid generated. Examples include B(C 6 F 5 ) 4 - , BF 4 - and other boron - based anions, (Rf) n PF 6-n - , PF 3 (C 2 F 5 ) 3- , PF 6 - and other phosphorus - based anions, SbF 6 - and other antimony - based anions, other carboxylic acid anions, sulfonic acid anions, etc.

[0663] 〔Iodine salt〕

[0664] In the present invention, the iodine salt represents a salt of an iodine cation and an anion. As the anion, the same anions as those in the sulfonium salt described above can be exemplified, and the preferred modes are also the same.

[0665] - Iodine cation -

[0666] As the iodine cation, a diaryliodine cation is preferred.

[0667] Moreover, as the iodine cation, the cation represented by the following formula (104) is preferred.

[0668] [Chemical formula 49]

[0669]

[0670] In formula (104), R 11 and R 12 each independently represent a hydrocarbon group.

[0671] R 11 and R 12 each independently are preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and still further preferably a phenyl group.

[0672] R 11 and R 12It may have substituents. Examples of the substituents include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among them, as the substituent, it preferably has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0673] R 11 and R 12 may be the same group or different groups. From the viewpoint of synthesis suitability, they are preferably the same group.

[0674] [Phosphonium salt]

[0675] In the present invention, the phosphonium salt represents a salt of a phosphonium cation and an anion. As the anion, the same anions as those in the sulfonium salt described above can be exemplified, and the preferred modes are also the same.

[0676] -Phosphonium cation-

[0677] As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.

[0678] Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred.

[0679] [Chemical formula 50]

[0680]

[0681] In formula (105), R 13 ~R 16 each independently represents a hydrogen atom or a hydrocarbon group.

[0682] R 13 ~R 16 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and still further preferably a phenyl group.

[0683] R 13 ~R 16 may have substituents. Examples of the substituents include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among them, as the substituent, it preferably has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0684] R 13 ~R 16They may be the same group or different groups. From the viewpoint of synthesis suitability, they are preferably the same group.

[0685] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, still more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and still even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition.

[0686] The photoacid generator may be used alone or in combination of two or more. When used in combination of two or more, the total amount of these is preferably within the above range.

[0687] In addition, in order to impart photosensitivity to a desired light source, it is preferably used in combination with a sensitizer.

[0688] In addition, it is also one of the preferred embodiments of the present invention that the resin composition of the present invention contains two or more polymerization initiators as the polymerization initiator.

[0689] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photo radical polymerization initiator and the above-mentioned photoacid generator.

[0690] By containing a photopolymerization initiator and a thermal polymerization initiator described later, there are cases where pattern formation based on exposure can be performed, radical polymerization becomes easier during curing in the subsequent heating step, and properties such as chemical resistance are improved.

[0691] As the content ratio when containing a photopolymerization initiator and a thermal polymerization initiator described later, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0692] By containing a photo radical polymerization initiator and a photoacid generator, there are cases where properties such as resolution are improved.

[0693] As the content ratio when containing a photopolymerization initiator and a photoacid generator, the content of the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total content of the photopolymerization initiator and the photoacid generator.

[0694] 〔Thermal polymerization initiator〕

[0695] As the thermal polymerization initiator, for example, a thermal radical polymerization initiator can be cited. A thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, so the solvent resistance can be further improved.

[0696] As a thermal free radical polymerization initiator, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554 can be cited, and the content is incorporated into this specification.

[0697] 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 with respect to the total solid content of the resin composition. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0698] <Base generator>

[0699] 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. As preferred base generators, thermal base generators and photo base generators can be cited.

[0700] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferred that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, so that it becomes a substance with good mechanical properties or chemical resistance of the cured product. For example, the performance of the interlayer insulating film for the rewiring layer contained in the semiconductor package becomes good.

[0701] The base generator may be an ionic base generator or a non-ionic base generator. As the base generated from the base generator, for example, secondary amines and tertiary amines can be cited.

[0702] The base generator is not particularly limited, and known base generators can be used. As known base generators, for example, 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-aminobenzophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxy imide compounds, etc. can be cited.

[0703] As a specific example of the non-ionic base generator, compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355 can be cited. The above description is incorporated into this specification.

[0704] As the base generator, the following compounds can be cited, but are not limited thereto.

[0705] [Chemical Formula 51]

[0706]

[0707] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

[0708] As specific examples of preferred compounds of the ionic base generator, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002 can be cited.

[0709] As specific examples of the ammonium salt, the following compounds can be cited, but are not limited thereto.

[0710] [Chemical Formula 52]

[0711]

[0712] As specific examples of the imine salt, the following compounds can be cited, but are not limited thereto.

[0713] [Chemical Formula 53]

[0714]

[0715] Moreover, as the base generator, from the viewpoints of storage stability and deprotection and generation of base during curing, an amine in which the amino group is protected by a tert-butoxycarbonyl group is preferred.

[0716] 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 - piperidyl)-2 - propanol, 1,4 - butanediol bis(3 - aminopropyl)ether, 1,2 - bis(2 - aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14 - diamino - 3,6,9,12 - tetraoxatetradecane, 1 - aza - 15 - crown 5 - ether, diethylene glycol bis(3 - aminopropyl)ether, 1,11 - diamino - 3,6,9 - trioxaundecane, or amino acids and compounds in which the amino group of the derivative is protected by a tert - butoxycarbonyl group, but are not limited to these.

[0717] When the resin composition contains a base - generating agent, the content of the base - generating agent is preferably 0.1 to 50 parts by mass with respect 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, 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, still more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0718] One kind or two or more kinds of base - generating agents can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0719] <Solvent>

[0720] The resin composition of the present invention preferably contains a solvent.

[0721] As the solvent, known solvents can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0722] As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, 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.)), 3-alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0723] As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are preferred ethers.

[0724] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. are preferred ketones.

[0725] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and cyclic terpenes such as limonene are preferred cyclic hydrocarbons.

[0726] As sulfoxides, for example, dimethyl sulfoxide is a preferred sulfoxide.

[0727] As amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0728] As ureas, preferred ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0729] As alcohols, preferred alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol, etc.

[0730] Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., a method of mixing two or more kinds is also preferred.

[0731] In the present invention, it is preferred to select one solvent 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-dimethylpropanamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds. Particularly preferred is to use dimethyl sulfoxide and γ-butyrolactone together, dimethyl sulfoxide and γ-valerolactone together, 3-methoxy-N,N-dimethylpropanamide and γ-butyrolactone together, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone and dimethyl sulfoxide together, or N-methyl-2-pyrrolidone and ethyl lactate together. A method of further adding about 1 to 10% by mass of toluene relative to the total mass of the solvent to these mixed solvents is also one of the preferred methods of the present invention.

[0732] In particular, from the viewpoint of storage stability of the resin composition and the like, a mode in which γ-valerolactone is included as a solvent is also one of the preferred modes of the present invention. In this mode, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. And, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as a specific resin contained in the resin composition.

[0733] Moreover, in the case of using dimethyl sulfoxide and γ-valerolactone in combination, it is preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably contains 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and still more preferably contains 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0734] From the viewpoint of coatability, the content of the solvent is preferably set to an amount such that the total solid content concentration of the resin composition of the present invention becomes 5 to 80% by mass, more preferably set to an amount that becomes 5 to 75% by mass, still more preferably set to an amount that becomes 10 to 70% by mass, and even more preferably set to an amount that becomes 20 to 70% by mass. The solvent content can be adjusted according to the required thickness of the coating film and the coating method. In the case of containing two or more solvents, it is preferably within the above range in total.

[0735] <Metal adhesion improver>

[0736] From the viewpoint of improving the adhesion to metal materials used in electrodes, wirings, etc., the resin composition of the present invention preferably contains a metal adhesion improver. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion 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, etc.

[0737] 〔Silane coupling agent〕

[0738] 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 Application Laid-Open No. 2018-173573 are cited, and these are incorporated into the present specification. Further, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group. Further, the following R may be a structure derived from a blocking agent in a blocked isocyanate group. As the blocking agent, it can be selected according to the dissociation temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. For example, from the viewpoint of setting the dissociation temperature to 160 to 180°C, caprolactam or the like is preferable. As a commercially available product of such a compound, X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) etc. can be cited.

[0739] [Chemical formula 54]

[0740]

[0741] As other silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride can be cited. These can be used alone or in combination of two or more.

[0742] Further, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyls can also be used.

[0743] Examples of the compound of this oligomer type include compounds containing a repeating unit represented by the following formula (S-1).

[0744] [Chemical formula 55]

[0745]

[0746] 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.

[0747] R S1 Preferably has a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, etc. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isopropyl 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, a (meth)acryloyloxy group, etc. Preferably, it is vinylphenyl, a (meth)acrylamide group or a (meth)acryloyloxy group, more preferably vinylphenyl or a (meth)acryloyloxy group, and further preferably a (meth)acryloyloxy group.

[0748] R S2 Is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.

[0749] n represents an integer of 0 to 2, and is preferably 1.

[0750] Here, the structures of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound may be the same respectively.

[0751] Here, among the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, it is preferable that n is 1 or 2 in at least one, more preferably n is 1 or 2 in at least two, and further preferably n is 1 in at least two.

[0752] As this oligomer type compound, commercially available products can be used. Examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0753] 〔Aluminum-based adhesion promoter〕

[0754] Examples of the aluminum-based adhesion promoter include aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), aluminum ethyl acetoacetate diisopropyl ester, etc.

[0755] As other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the thioether compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these are incorporated into this specification.

[0756] With respect to 100 parts by mass of a specific resin, the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass. By setting it to be above the above lower limit value, the adhesion between the pattern and the metal layer becomes good, and by setting it to be below the above upper limit value, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. In the case of using two or more kinds, it is preferable that their total is within the above range.

[0757] <Migration inhibitor>

[0758] The resin composition of the present invention preferably further contains a migration inhibitor. By containing a 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 inhibited.

[0759] There is no particular limitation on the migration inhibitor, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and thioalkyl groups, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole-based compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0760] Among them, the resin composition of the present invention preferably contains an azole compound.

[0761] The azole compound is a compound containing an azole structure, and the azole structure refers to a 5-membered ring structure containing a nitrogen atom as a ring member, and preferably a 5-membered ring structure containing two or more nitrogen atoms as ring members. Specifically, examples of the azole structure include an imidazole structure, a triazole structure, and a tetrazole structure. Such as benzimidazole, benzotriazole, etc., and these structures can form polycyclic rings with other ring structures through condensation or the like.

[0762] Furthermore, as the compound having an azole structure, a compound in which a group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure is also preferred.

[0763] [Chemical formula 56]

[0764]

[0765] In formula (R-1), R 1 represents a monovalent organic group, and * represents a bonding position to the azole structure.

[0766] In formula (R-2), R 2 represents a hydrogen atom or a monovalent organic group, R 3 represents a monovalent organic group, and * represents a bonding position to the azole structure.

[0767] In formula (R-1), R 1 It is preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O) 2 - and -NR N - is a group represented by a bond of at least one group in R. N As described above.

[0768] The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

[0769] And, R 1 The total number of carbon atoms is preferably 1-30, preferably 2-25, more preferably 3-20.

[0770] R 1 The bonding position with the carbonyl group in formula (R-1) is preferably a hydrocarbon group or -NR N -.

[0771] In the formula (R-1), * represents a bonding position to the azole structure, preferably a bonding position to a carbon atom which is a ring member of the azole structure.

[0772] In formula (R-2), R 2 Preferred is a hydrogen atom.

[0773] In R 2 When R is a monovalent organic group, 2 It is preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O) 2 - and -NR N - is a group represented by a bond of at least one group in R. N As described above.

[0774] As the above-mentioned hydrocarbon group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these is preferred.

[0775] And, when R 2 is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and still more preferably 3 to 20.

[0776] When R 2 is a monovalent organic group, the bonding position of R 2 to the nitrogen atom in formula (R-2) is preferably a hydrocarbon group or -C(=O)-.

[0777] In formula (R-2), R 3 is preferably a hydrocarbon group or a group represented by a bond of a hydrocarbon group and at least one group selected from -O-, -C(=O)-, -S-, -S(=O) 2 -, and -NR N -. R N is as described above.

[0778] As the above-mentioned hydrocarbon group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these is preferred.

[0779] And, when R 3 is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and still more preferably 3 to 20.

[0780] R 3 in the bonding position to the nitrogen atom in formula (R-2) is preferably a hydrocarbon group or -C(=O)-.

[0781] In formula (R-2), * represents the bonding position to the azole structure, and is preferably the bonding position to a carbon atom that is a ring member of the azole structure.

[0782] As the migration inhibitor, an ion scavenger that scavenges anions such as halogen ions can also be used.

[0783] As other migration inhibitors, rust preventives described in paragraph 0094 of Japanese Unexamined Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Unexamined Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Unexamined Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Unexamined Patent Application Publication No. 2012-194520, compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and these contents are incorporated into this specification.

[0784] As a specific example of the migration inhibitor, the following compounds can be cited.

[0785] [Chemical Formula 57]

[0786]

[0787] 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 further preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0788] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferable that their total is within the above range.

[0789] [Polymerization inhibitor]

[0790] 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, metal compounds, etc.

[0791] Specific examples of the compound as the polymerization inhibitor include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the compounds used in the following examples. This content is incorporated into the present specification.

[0792] 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 further preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0793] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, it is preferable that their total is within the above range.

[0794] [Light absorber]

[0795] The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

[0796] Whether a certain compound a contained in the resin composition corresponds to a light absorber (that is, whether the absorbance at the exposure wavelength decreases upon exposure) can be determined by the following method.

[0797] First, prepare a solution of Compound a at the same concentration as that contained in the resin composition, and measure the molar extinction coefficient of Compound a at the wavelength of the exposure light (mol -1 ·L·cm -1 , also referred to as "molar extinction coefficient 1"). To reduce the influence of changes such as a decrease in the molar extinction coefficient of Compound a, the above measurement is carried out rapidly. Regarding the solvent in the above solution, when the resin composition contains a solvent, use that solvent; when the resin composition does not contain a solvent, use N-methyl-2-pyrrolidone.

[0798] Next, irradiate the solution of Compound a with the exposure light. For 1 mole of Compound a, the cumulative exposure dose is 500 mJ.

[0799] After that, use the exposed solution of Compound a to measure the molar extinction coefficient of Compound a at the wavelength of the exposure light (mol -1 ·L·cm -1 , also referred to as "molar extinction coefficient 2").

[0800] From the above molar extinction coefficient 1 and molar extinction coefficient 2, calculate the attenuation rate (%) according to the following formula. When the attenuation rate (%) is 5% or more, it is determined that Compound a is a compound whose absorbance at the exposure wavelength becomes smaller through exposure (i.e., a photoabsorbent).

[0801] Attenuation rate (%) = 1 - molar extinction coefficient 2 / molar extinction coefficient 1 × 100

[0802] The above attenuation rate is preferably 10% or more, more preferably 20% or more. Moreover, the lower limit of the above attenuation rate is not particularly limited, and 0% or more is sufficient.

[0803] As the wavelength of the above exposure light, when the resin composition is used to form a photosensitive film, it is sufficient that it is the wavelength at which the photosensitive film is exposed.

[0804] Moreover, as the wavelength of the above exposure light, it is preferably the wavelength at which the photoinitiator contained in the resin composition has sensitivity. That the photoinitiator has sensitivity to a certain wavelength means that polymerization initiating species are generated when the photoinitiator is exposed at a certain wavelength.

[0805] As the wavelength of the above exposure light, in terms of the relationship with the light source, examples include (1) semiconductor lasers (wavelengths 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), broadband (three wavelengths of g, h, and i rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) the second harmonic of YAG laser 532 nm, the third harmonic 355 nm, etc.

[0806] Regarding the wavelength of the exposure light, for example, as long as a wavelength at which the photoinitiator has sensitivity is selected, h rays (wavelength 405 nm) or i rays (wavelength 365 nm) are preferred, and i rays (wavelength 365 nm) are more preferred.

[0807] The photoabsorbent can be a compound that generates a radical polymerization initiation species upon exposure, but from the viewpoints of resolution and chemical resistance, a compound that does not generate a radical polymerization initiation species upon exposure is preferred.

[0808] It can be determined whether the photoabsorbent is a compound that generates a radical polymerization initiation species upon exposure by the following method.

[0809] Prepare a solution containing the photoabsorbent and the radical crosslinking agent at the same concentration as that contained in the resin composition. When the resin composition contains a radical crosslinking agent, as the radical crosslinking agent in the above solution, the same compound as the radical crosslinking agent 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 photoabsorbent.

[0810] After that, irradiation with exposure light is performed. The cumulative amount of the exposure dose is set to 500 mJ.

[0811] After exposure, for example, the polymerization of the polymerizable compound is judged by high-performance liquid chromatography. When the ratio of the molar amount of the polymerizable compound that has polymerized to the total molar amount of the polymerizable compound is 10% or less, it is judged that the photoabsorbent is a compound that does not generate a radical polymerization initiation species upon exposure.

[0812] The above ratio of the molar amount is preferably 5% or less, more preferably 3% or less. Moreover, the lower limit of the above ratio of the molar amount is not particularly limited and can be 0%.

[0813] When using the resin composition to form a photosensitive film, the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed.

[0814] Moreover, as the wavelength of the exposure light, the wavelength at which the photoinitiator contained in the resin composition has sensitivity is preferred.

[0815] As the compound that generates a radical polymerization initiation species by exposure, the same compounds as the above photo radical initiators can be cited. When the composition contains a photo radical initiator as a light absorber, the compound with the lowest polymerization initiation ability of the generated radical species is used as the light absorber, and the others are used as photoinitiators.

[0816] As the compound that does not generate a radical polymerization initiation species by exposure, in addition to photoacid generators and photobase generators, pigments whose absorption wavelength changes by exposure can be cited.

[0817] Among them, as the light absorber, naphthoquinone diazide or a pigment whose absorbance changes by exposure is preferred, and naphthoquinone diazide is more preferred.

[0818] And, as the light absorber, for example, a combination of a photoacid generator or a photobase generator and a compound whose absorbance at the exposure wavelength decreases according to pH can also be considered.

[0819] [Naphthoquinone diazide]

[0820] As the naphthoquinone diazide, a compound that generates indenecarboxylic acid by exposure and whose absorbance at the exposure wavelength decreases can be cited, and a compound having a 1,2-naphthoquinone diazide structure is preferred.

[0821] As the naphthoquinone diazide, naphthoquinone diazide sulfonic acid ester of a hydroxy compound is preferred.

[0822] As the above hydroxy compound, a compound represented by any one of the following formulas (H1) to (H6) is preferred.

[0823] [Chemical formula 58]

[0824]

[0825] In formula (H1), R 1 and R 2 each independently represent a monovalent organic group, R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group, and 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.

[0826] In formula (H2), Z represents a tetravalent organic group, and L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent organic group, and R 5 , R 6 , R 7 and R 8 each independently represent a monovalent organic group, n3, n4, n5, and n6 are each independently an integer from 0 to 3, m3, m4, m5, and m6 are each independently an integer from 0 to 2, and at least one of m3, m4, m5, and m6 is 1 or 2.

[0827] In formula (H3), R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group, and L 5 each independently represent a divalent organic group, and n7 represents an integer from 3 to 8.

[0828] In formula (H4), L 6 represents a divalent organic group, and L 7 and L 8 each independently represent a divalent organic group containing an aliphatic tertiary carbon atom or quaternary carbon atom.

[0829] 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 represent a hydrogen atom, a halogen atom, or a monovalent organic group, and L 9 , L 10 and L 11 each independently represent a single bond or a divalent organic group, and m7, m8, m9, and m10 each independently represent an integer from 0 to 2, and at least one of m7, m8, m9, and m10 is 1 or 2.

[0830] In formula (H6), R 42 , R 43 , R 44 and R 45 each independently represent a hydrogen atom or a monovalent organic group, R 46 and R 47 each independently represent a monovalent organic group, n16 and n17 each independently represent an integer from 0 to 4, m11 and m12 each independently represent an integer from 0 to 4, and at least one of m11 and m12 is an integer from 1 to 4.

[0831] In formula (H1), R 1 and R 2 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. As the monovalent organic group for R 1 and R 2 , there may be mentioned a hydrocarbon group which may have a substituent, for example, an aromatic hydrocarbon group which may have a substituent such as a hydroxyl group.

[0832] In formula (H1), R 3 and R 4 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. As the monovalent organic group for R 3 and R 4 , there may be mentioned a hydrocarbon group which may have a substituent, for example, a hydrocarbon group which may have a substituent such as a hydroxyl group.

[0833] In formula (H1), n1 and n2 are each independently preferably 0 or 1, more preferably 0.

[0834] In formula (H1), m1 and m2 are both preferably 1.

[0835] The compound represented by formula (H1) is preferably any one of the compounds represented by formula (H1-1) to formula (H1-5).

[0836] [Chemical formula 59]

[0837]

[0838] In formula (H1-1), R 21 , R 22 and R 23 each independently represent 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).

[0839] [Chemical formula 60]

[0840]

[0841] 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 the bonding position to other structures.

[0842] (In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.

[0843] In formula (H1-2), R24 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. R 30 represents a hydrogen atom or an alkyl group.

[0844] In formula (H1-3), R 25 , R 26 , R 27 and R 28 each independently represent a monovalent organic group, preferably a hydrogen atom, an alkyl group or the group represented by the above formula (R-1).

[0845] In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, preferably 0 or 1.

[0846] As the compound represented by formula (H1-1), preferably any one of the compounds represented by the following formula (H1-1-1) to formula (H1-1-4).

[0847] As the compound represented by formula (H1-2), preferably the compound represented by the following formula (H1-2-1) or (H1-2-2).

[0848] As the compound represented by formula (H1-3), preferably any one of the compounds represented by the following formula (H1-3-1) to formula (H1-3-3).

[0849] [Chemical formula 61]

[0850]

[0851] In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, more preferably any one of the groups represented by the following formula (Z-1) to (Z-4). In the following formula (Z-1) to (Z-4), * represents the bonding position with other structures.

[0852] [Chemical formula 62]

[0853]

[0854] In formula (H2), L 1 , L 2 , L 3 and L 4 each independently are preferably a single bond or a methylene group.

[0855] In formula (H2), R 5 , R 6 , R 7 and R 8 each independently are preferably an organic group having 1 to 30 carbon atoms.

[0856] In formula (H2), n3, n4, n5, and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0857] In formula (H2), m3, m4, m5, and m6 are each independently preferably 1 or 2, more preferably 1.

[0858] As the compound represented by formula (H2), compounds having the following structures can be exemplified.

[0859] [Chemical formula 63]

[0860]

[0861] 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.

[0862] In formula (H3), L 5 each independently is preferably a group represented by the following formula (L-1).

[0863] [Chemical formula 64]

[0864]

[0865] 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 the bonding position to other structures.

[0866] In formula (H3), n7 is preferably an integer of 4 to 6.

[0867] As the compound represented by formula (H3), the following compounds can be exemplified. In the following formulas, n each independently represents an integer of 0 to 9.

[0868] [Chemical formula 65]

[0869]

[0870] In formula (H4), L 6 is preferably -C(CF 3 ) 2 -, -S(=O) 2 -, or -C(=O)-.

[0871] In formula (H4), L 7 and L 8 each independently are preferably a divalent organic group having 2 to 20 carbon atoms.

[0872] As the compound represented by formula (H4), the following compounds can be mentioned.

[0873] [Chemical formula 66]

[0874]

[0875] In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group.

[0876] In formula (H5), L 9 , L 10 and L 11 are each independently preferably a single bond, -O-, -S-, -S(=O) 2 -, -C(=O)-, -C(=O)O-, a cyclopentylene group, a cyclohexylene group, a phenylene group or a divalent organic group having 1 to 20 carbon atoms, more preferably any one of the groups represented by the following formula (L-2) to formula (L-4).

[0877] [Chemical formula 67]

[0878]

[0879] In formula (L-2) to formula (L-4), R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, R 34 , R 35 , R 36 and R 37 each independently represent a hydrogen atom or an alkyl group, n15 is an integer of 1 to 5, R 38 , R 39 , R 40 and R 41 each independently represent a hydrogen atom or an alkyl group, * represents the bonding position to other structures.

[0880] As the compound represented by formula (H5), the following compounds can be mentioned.

[0881] [Chemical formula 68]

[0882]

[0883] In formula (H6), R42 、 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, still more preferably an alkyl group having 1 to 4 carbon atoms.

[0884] In formula (H6), R 46 and R 47 are each independently preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group.

[0885] In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0886] In formula (H6), n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3.

[0887] Examples of the compound represented by formula (H6) include the following compounds.

[0888] [Chemical formula 69]

[0889]

[0890] In addition, examples of the hydroxy compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone,

[0891] polyhydroxyphenylalkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentanone, 2,3,4-trihydroxyphenylhexanone,

[0892] 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,

[0893] Propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate and other polyhydroxybenzoates,

[0894] 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)arenes,

[0895] Ethylene bis(3,5-dihydroxybenzoate), ethylene bis(3,4,5-trihydroxybenzoate) and other alkylene bis(polyhydroxybenzoates),

[0896] 2,3,4-Biphenyltriol, 3,4,5-biphenyltriol, 3,5,3′,5′-biphenyltetrol, 2,4,2′,4′-biphenyltetrol, 2,4,6,3′,5′-biphenylpentol, 2,4,6,2′,4′,6′-biphenylhexol, 2,3,4,2′,3′,4′-biphenylhexol and other polyhydroxybiphenyls,

[0897] 4,4′-Thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides,

[0898] 2,2′,4,4′-Tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl)ethers,

[0899] 2,2′,4,4′-Tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl)sulfoxides,

[0900] 2,2′,4,4′-Diphenyl sulfone and other bis(polyhydroxyphenyl)sulfones,

[0901] 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-methoxyphenol, 4,4′-(3,4-diol-benzylidene)bis[2,6-dimethylphenol], 4,4′-[(2-hydroxyphenyl)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 polyhydroxyethylbenzenes;

[0902] 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,5′,6′-tetrol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,7,5′,6′,7′-hexol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,4′,5′,6′-hexol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,5′,6′,7′-hexol and other polyhydroxyspirobi-indanes; 2,4,4-trimethyl-2′,4′,7′-trihydroxyflavane and other polyhydroxyflavanes;

[0903] 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3′,4′,5′,6′-tetrahydroxybis[phthalide-3,9′-xanthene] and other polyhydroxyphthalides; morin, quercetin, rutin and other flavonoid pigments;

[0904] 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-dipropyl-4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α, α', α''-tris(3,5-diisopropyl-4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α, α', α''-tris(3,5-dibutyl-4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α, α', α''-tris(3-methyl-4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α, α', α''-tris(3-methoxy-4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α, α', α''-tris(2,4-dihydroxyphenyl)-1,3,5-triisopropylbenzene, 1,3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxybenzylthiomethyl)mesitylene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α, α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4'-hydroxyphenyl)ethyl]-3-[α, α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4'-hydroxyphenyl)ethyl]-4-[α, α'-bis(3'',5''-dimethyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α', α'-bis(3''-methyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α', α'-bis(3''-methoxy-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4-[α', α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α', α'-bis(4''-hydroxyphenyl)ethyl]benzene and other 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 other polyhydroxy compounds described in Japanese Patent Laid-Open No. 5-224410, 1,2,2,3-tetrakis(p-hydroxyphenyl)propane, 1,3,3,5-tetrakis(p-hydroxyphenyl)pentane and other poly(hydroxyphenyl)alkanes described in Japanese Patent Laid-Open No. 5-303200 and EP-530148

[0905] Bis(2,3,4-trihydroxybenzoyl)benzene, 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)paraxylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl)mesitylene,

[0906] 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)-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-methylphenyl)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)-(4-hydroxy-3-methoxyphenyl)methane, etc.

[0907] In addition, low nuclear bodies of phenolic resins such as novolac resins can also be used.

[0908] Examples of naphthoquinone diazosulfonic acids include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid, 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, etc., and these can be used in combination.

[0909] The method for producing a naphthoquinone diazosulfonic acid ester of a hydroxy compound is not particularly limited. For example, it can be obtained by subjecting naphthoquinone diazosulfonic acid to sulfonyl chloride using chlorosulfonic acid or thionyl chloride, and subjecting the obtained naphthoquinone diazosulfonyl chloride to a condensation reaction with the hydroxy compound.

[0910] For example, it can be obtained by reacting a hydroxy compound with a specified amount of naphthoquinone diazosulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, followed by washing with water and drying the resulting product.

[0911] The esterification rate in the naphthoquinone diazosulfonate is not particularly limited, preferably 10% or more, more preferably 20% or more. Moreover, the upper limit of the above esterification rate is not particularly limited and can be 100%.

[0912] The above esterification rate can be determined as the ratio of the esterified groups in the hydroxyl groups of the hydroxy compound and confirmed by 1 H-NMR or the like.

[0913] In addition, as the light absorber, the compounds described in paragraphs 0088 to 0108 of Japanese Patent Laid-Open No. 2019-206689 can also be used.

[0914] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass.

[0915] <Other Additives>

[0916] The resin composition of the present invention may contain various additives as needed within the range where the effects of the present invention can be obtained. For example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-agglomerants, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (such as defoamers, flame retardants, etc.). In addition, the resin composition of the present invention may also contain urea compounds, carbodiimide compounds, or isourea compounds. By appropriately containing these components, properties such as film physical properties can be adjusted. Regarding these components, for example, reference can be made to the descriptions in paragraphs 0183 and subsequent paragraphs of Japanese Patent Laid-Open No. 2012-003225 (corresponding to paragraphs 0237 and subsequent paragraphs of US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Laid-Open No. 2008-250074, etc., and these contents are incorporated herein. When these additives are incorporated, it is preferable to set the total content thereof to 3% by mass or less of the solid content of the resin composition of the present invention.

[0917] As these other additives, the compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated herein.

[0918] 〔Inorganic Particles〕

[0919] As the inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be cited.

[0920] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0921] The above average particle diameter of the inorganic particles is the primary particle diameter and is the volume average particle diameter. The volume average particle diameter can be measured, for example, by the dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0922] In the case where it is difficult to perform the above measurement, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, or the laser diffraction / scattering method.

[0923] [Organic titanium compound]

[0924] Since the resin composition contains an organic titanium compound, a resin layer excellent in chemical resistance can be formed even when curing is performed at a low temperature.

[0925] As the organic titanium compound that can be used, compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond can be cited.

[0926] Specific examples of the organic titanium compound are shown in the following I) to VII).

[0927] I) Titanium chelate compound: From the viewpoint of excellent storage stability of the resin composition and good curing patterns, a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples are bis(triethanolamine)titanium diisopropoxide, bis(2,4-pentanedionato)titanium di(n-butoxide), bis(2,4-pentanedionato)titanium diisopropoxide, bis(4,4,5,5-tetramethyl-1,3-hexanedionato)titanium diisopropoxide, bis(ethyl acetoacetato)titanium diisopropoxide, etc.

[0928] II) Tetraalkoxytitanium compound: For example, titanium tetra(n-butoxide), titanium tetraethanolate, titanium tetra(2-ethylhexoxide), titanium tetra(isobutoxide), titanium tetra(isopropoxide), titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetra(stearate), titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0929] III) Titanium cyclopentadienyl compounds: such as pentamethylcyclopentadienyltitanium trimethanol, 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.

[0930] IV) Monoalkoxy titanium compounds: such as titanium isopropoxide tris(dioctyl phosphate), titanium isopropoxide tris(dodecylbenzenesulfonate), etc.

[0931] V) Titanium oxide compounds: such as titanium oxide bis(acetylacetonate), titanium oxide bis(tetramethylheptanedionate), titanium oxide phthalocyanine, etc.

[0932] VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate, etc.

[0933] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0934] Among them, as the organotitanium compound, from the viewpoint of better chemical resistance, at least one compound selected from the above I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanium cyclopentadienyl compounds is preferred. In particular, bis(ethyl acetoacetate)titanium diisopropoxide, titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0935] When an organotitanium compound is contained, relative to 100 parts by mass of a specific resin, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass. 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 it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0936] 〔Antioxidant〕

[0937] By containing an antioxidant as an additive, the elongation property of the cured film or the adhesion to a metal material can be improved. As the antioxidant, phenolic compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As a specific example of the antioxidant, the compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189 are cited, and this content is incorporated into this specification.

[0938] With respect to 100 parts by mass of a specific resin, the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. By setting the addition amount to 0.1 part by mass or more, it is easy to obtain the effect of improving the elongation characteristics or the adhesion to a metal material even in a high-temperature and high-humidity environment, and by setting it to 10 parts by mass or less, for example, the sensitivity of the resin composition is improved by the interaction with a photosensitizer. One type of antioxidant may be used alone, or two or more types may be used. In the case of using two or more types, it is preferable that the total amount thereof is within the above range.

[0939] <Properties of the resin composition>

[0940] The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 / s to 12,000 mm 2 / s, more preferably 2,000 mm 2 / s to 10,000 mm 2 / s, and further preferably 2,500 mm 2 / s to 8,000 mm 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 1,000 mm 2 / s or more, it is easy to coat with the film thickness required for a rewiring insulating film, and if it is 12,000 mm 2 / s or less, a coating film with excellent coating surface condition can be obtained.

[0941] <Restrictions on the substances contained in the resin composition>

[0942] 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. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0943] As a method for maintaining the water content, examples include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0944] 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 the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but excluding metals contained as complexes of organic compounds and metals. In the case of containing multiple metals, it is preferable that the total of these metals is within the above range.

[0945] And, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention through a filter, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.

[0946] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosiveness, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm. Among them, the halogen atoms present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. The total of chlorine atoms and bromine atoms or chloride ions and bromide ions is preferably within the above ranges respectively.

[0947] As a method for adjusting the content of halogen atoms, ion exchange treatment, etc. can be preferably cited.

[0948] As a storage container for the resin composition of the present invention, conventionally known storage containers 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, multilayer bottles composed of 6 types of 6 layers of resin for the container inner wall and bottles with a 7-layer structure formed of 6 types of resin are also preferably used. As such containers, for example, the containers described in Japanese Unexamined Patent Application Publication No. 2015-123351 can be cited.

[0949] <Cured product of resin composition>

[0950] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0951] The cured product of the present invention is a cured product obtained by curing the resin composition.

[0952] The curing of the resin composition is preferably carried out by heating, more preferably the heating temperature is 120°C to 400°C, still more 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 can be selected according to the use, such as film-like, rod-like, spherical, granular, etc. In the present invention, the cured product is preferably film-like. Through the pattern processing of the resin composition, the shape of the cured product can also be selected according to uses such as forming a protective film on the wall surface, forming a through-hole for conduction, adjusting impedance, capacitance or internal stress, and imparting heat dissipation function. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0953] When curing the resin composition of the present invention, the shrinkage rate is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition and can be calculated by the following formula.

[0954] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0955] <Properties of the cured product of the resin composition>

[0956] 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 still more preferably 90% or more. If it is 70% or more, the cured product sometimes has excellent mechanical properties.

[0957] 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 still more preferably 50% or more.

[0958] 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 still more preferably 230 °C or higher.

[0959] <Preparation of the resin composition>

[0960] The resin composition of the present invention can be prepared by mixing the above-mentioned respective components. The mixing method is not particularly limited and can be carried out by a conventionally known method.

[0961] As the mixing method, mixing using a stirring blade, mixing using a ball mill, mixing by rotating a tank, etc. can be cited.

[0962] The temperature during mixing is preferably 10 to 30 °C, more preferably 15 to 25 °C.

[0963] For the purpose of removing foreign matters such as dust or fine particles from the resin composition of the present invention, filtration using a filter is preferably performed. Regarding the pore size of the filter, for example, it is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). A filter that has been pre-cleaned with an organic solvent can be used. In the filter filtration step, multiple filters can be connected in series or in parallel and used. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage in series can be cited. Also, various materials can be filtered multiple times. When filtering multiple times, it can be a cyclic filtration. Also, filtration can be performed after pressurization. When filtration is performed after pressurization, the pressure applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, further preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0964] In addition to filtration using a filter, impurity removal treatment using an adsorbent material can also be performed. Filtration using a filter and impurity removal treatment using an adsorbent material can also be combined. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be cited.

[0965] After filtration using a filter, a step of degassing the resin composition filled in a bottle under reduced pressure can be implemented.

[0966] (Method for manufacturing a cured product)

[0967] The method for manufacturing 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.

[0968] The method for manufacturing a cured product more preferably includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern.

[0969] The method for manufacturing a cured product particularly preferably includes at least one of the above-mentioned film forming step, the above-mentioned exposure step, the above-mentioned development step, a heating step of heating the pattern obtained by the development step, and a post-exposure step of exposing the pattern obtained by the development step.

[0970] Moreover, the method for producing the cured product preferably includes the above-described film-forming step and the step of heating the film.

[0971] Hereinafter, the detailed content of each step will be described.

[0972] <Film-forming step>

[0973] The resin composition of the present invention can be used in a film-forming step of applying it to a substrate to form a film.

[0974] The method for producing the cured product of the present invention preferably includes a film-forming step of applying the resin composition to a substrate to form a film.

[0975] 〔Substrate〕

[0976] The type of the substrate can be appropriately determined according to the use and is not particularly limited. Examples of the substrate include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflection films, and metal substrates such as Ni, Cu, Cr, and Fe (for example, any one of a substrate formed of a metal and a substrate formed with a metal layer by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDP). In particular, the substrate is preferably a semiconductor substrate, more preferably a silicon substrate, a Cu substrate, and a mold substrate.

[0977] A bonding layer or an oxide layer or the like formed of hexamethyldisilazane (HMDS) or the like can be provided on the surface of these substrates.

[0978] The shape of the substrate is not particularly limited and can be a circular shape or a rectangular shape.

[0979] Regarding the size of the substrate, if it is a circular shape, for example, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm. If it is a rectangular shape, for example, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.

[0980] As the substrate, for example, a plate shape can be used, and a panel-shaped substrate (substrate) is preferably used.

[0981] When forming a film by applying the resin composition on the surface of a resin layer (for example, a layer composed of a cured product) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0982] As a method for applying the resin composition to the substrate, coating is preferred.

[0983] As the method to be applied, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spraying method, spin coating method, slot coating method, inkjet method, etc. can be cited. From the viewpoint of the uniformity of the film thickness, spin coating method, slot coating method, spraying method or inkjet method is preferred, and from the viewpoints of the uniformity of the film thickness and productivity, spin coating method and slot coating method are more preferred. By adjusting the solid content concentration or coating conditions of the resin composition according to the method to be applied, a film with a desired thickness can be obtained. Also, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating method, spraying method, inkjet method, etc. are preferred, and for a rectangular substrate, slot coating method, spraying method, inkjet method, etc. are preferred. In the case of spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[0984] Also, a method of transferring the coating film previously imparted and formed on the temporary support by the above imparting method to the substrate can be applied.

[0985] Regarding the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Laid-Open No. 2006-047592 can also be preferably used.

[0986] Also, a step of removing the excess film at the end of the substrate can be performed. Examples of such steps include edge bead rinse (EBR), backside rinse, etc.

[0987] A pre-wetting step can also be adopted: before coating the resin composition on the substrate, various solvents are coated on the substrate, and after improving the wettability of the substrate, the resin composition is coated.

[0988] <Drying step>

[0989] After the film formation step (layer formation step), in order to remove the solvent, the above-mentioned film can be subjected to a step of drying the formed film (layer) (drying step).

[0990] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film formation step.

[0991] The above drying step is preferably performed after the film formation step and before the exposure step.

[0992] The drying temperature of the film in the drying process is preferably 50°C to 150°C, more preferably 70°C to 130°C, and further preferably 90°C to 110°C. Also, drying can be carried out under reduced pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0993] <Exposure process>

[0994] The above-mentioned film can be used in an exposure process for selectively exposing the film.

[0995] The method for manufacturing a cured product may include an exposure process for selectively exposing the film formed by the film-forming process.

[0996] Selective exposure means exposing a part of the film. And, through selective exposure, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed on the film.

[0997] The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention. For example, in terms of the exposure energy conversion at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0998] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0999] Regarding the exposure wavelength, in terms of its relationship with the light source, examples include (1) semiconductor lasers (wavelengths 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 wavelength (3 wavelengths of g, h, and i rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonic of YAG laser 532 nm, third harmonic 355 nm, etc. Regarding 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.

[1000] The exposure method is not particularly limited, and any method for exposing at least a part of the film composed of the resin composition of the present invention can be used. Examples include exposure using a photomask, exposure using a laser direct imaging method, etc.

[1001] <Post-exposure heating process>

[1002] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[1003] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating process of heating the film exposed by the exposure process.

[1004] The post-exposure heating process can be carried out after the exposure process and before the development process.

[1005] The heating temperature in the post-exposure heating process is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[1006] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1007] Regarding the heating rate in the post-exposure heating process, from the temperature at the start of heating to the maximum heating temperature, it is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute.

[1008] Moreover, the heating rate can be appropriately changed during the heating process.

[1009] As the heating method in the post-exposure heating process, it is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used.

[1010] Also, during heating, it is preferably carried out in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[1011] <Development process>

[1012] The above-mentioned film after exposure can be used in a development process of forming a pattern by developing with a developer.

[1013] That is, the method for manufacturing the cured product of the present invention may include a development process of developing the film exposed by the exposure process with a developer to form a pattern.

[1014] By developing, one of the exposed part and the non-exposed part of the film is removed to form a pattern.

[1015] Here, the development of removing the non-exposed part of the film by the development process is called negative development, and the development of removing the exposed part of the film by the development process is called positive development.

[1016] 〔Developer〕

[1017] As the developer used in the development process, a developer containing an alkaline aqueous solution or an organic solvent can be cited.

[1018] When the developer is an alkaline aqueous solution, examples of the alkaline compound that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, they are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, it is TMAH. In the total mass of the developer, the content of the alkaline 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.

[1019] When the developer contains an organic solvent, as the organic solvent, the compounds described in paragraph 0387 of International Publication No. 2021 / 112189 can be used. This content is incorporated into this specification. Also, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can be preferably listed, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be preferably listed.

[1020] Also, when the developer contains an organic solvent, one kind of organic solvent can be used or two or more kinds can be used in combination. 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, and 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.

[1021] 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. Also, the above content can be 100% by mass.

[1022] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and a base generator. By at least one of the alkaline compound and the base generator in the developer penetrating into the pattern, the properties such as the elongation at break of the pattern may be improved.

[1023] As the basic compound, from the viewpoint of the reliability when remaining in the cured film (the adhesion to the substrate when further heating the cured product), an organic base is preferred.

[1024] As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred.

[1025] As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is not easily left in the cured film (the obtained cured product) is preferred. From the viewpoint of promoting cyclization, a compound with a residue amount that is not easily reduced by gasification or the like before heating is preferred.

[1026] Therefore, the boiling point of the basic compound is preferably 30°C to 350°C under normal pressure (101,325 Pa), more preferably 80°C to 270°C, and further preferably 100°C to 230°C.

[1027] 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.

[1028] For example, when the boiling point of the organic solvent is 100°C, the base used is preferably one having a boiling point of 80°C or higher, and more preferably 100°C or higher.

[1029] The developer may contain only one basic compound or two or more basic compounds.

[1030] 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 (1,5-diazabicyclo[4.3.0]non-5-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyl dicyclohexylamine, 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-diphenylethaneamine, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, etc.

[1031] The preferred form of the alkali generator is the same as that of the alkali generator contained in the above composition. In particular, the alkali generator is preferably a thermal alkali generator.

[1032] 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, based on 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.

[1033] When the basic compound or the alkali generator is solid in the environment where the developer is used, the content of the basic compound or the alkali generator is also preferably 70 to 100% by mass based on the total solid content of the developer.

[1034] The developer may contain only at least one of one kind of basic compound and an alkali generator, or may contain at least one of two or more kinds of basic compounds and an alkali generator. When at least one of the basic compound and the alkali generator is two or more kinds, it is preferably within the above range in total.

[1035] The developer may further contain other components.

[1036] Examples of other components include known surfactants or known antifoaming agents, etc.

[1037] 〔Supply method of developer〕

[1038] As long as the desired pattern can be formed, there is no particular limitation on the method of supplying the developer, and examples thereof include: a method of immersing a substrate having a film formed thereon in the developer; spin immersion development or a method of continuously supplying the developer to the film formed on the substrate using a nozzle. There is no particular limitation on the type of nozzle, and examples thereof include a straight nozzle, a spray nozzle, and an atomizing nozzle.

[1039] From the viewpoints of the permeability of the developer, the removability of the non-image portion, and the manufacturing efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using an atomizing nozzle is preferred. From the viewpoint of the permeability of the developer to the image portion, a method of supplying the developer using an atomizing nozzle is more preferred.

[1040] Moreover, the following procedure can be adopted: after continuously supplying the developer using a straight nozzle, the substrate is rotated to remove the developer from the substrate; after spin drying, the developer is continuously supplied again using a straight nozzle, and then the substrate is rotated to remove the developer from the substrate, and this procedure can be repeated multiple times.

[1041] As a method of supplying the developer in the developing step, examples include: a step of continuously supplying the developer to the substrate; a step of keeping the developer in a substantially stationary state on the substrate; a step of vibrating the developer on the substrate using ultrasonic waves or the like; and a step of combining them.

[1042] As the developing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is more preferred. The temperature of the developer during development is not particularly limited, and 10 to 45°C is preferred, and 18 to 30°C is more preferred.

[1043] In the developing step, after treatment with the developer, the pattern can be further cleaned (rinsed) using a rinsing liquid. Moreover, a method such as supplying the rinsing liquid before the developer in contact with the pattern is completely dried can also be adopted.

[1044] 〔Rinsing Liquid〕

[1045] When the developer is an alkaline aqueous solution, water can be used as the rinsing liquid, for example. In the case where the developer is a developer containing an organic solvent, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing liquid, for example.

[1046] As the organic solvent when the rinsing liquid contains an organic solvent, the same organic solvents as those exemplified when the above-mentioned developer contains an organic solvent can be cited.

[1047] The organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility of the pattern than the organic solvent contained in the developer.

[1048] When the rinsing liquid contains an organic solvent, one kind of organic solvent can be used or two or more kinds can be used in combination. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and still more preferably cyclohexanone or PGMEA.

[1049] When the rinsing liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the total mass of the rinsing liquid. Moreover, the organic solvent can be 100% by mass based on the total mass of the rinsing liquid.

[1050] The rinsing liquid may contain at least one of an alkaline compound and a base generator.

[1051] Although not particularly limited, when the developer contains an organic solvent, a mode in which the rinsing liquid contains at least one of an organic solvent, an alkaline compound, and a base generator is also one of the preferred modes of the present invention.

[1052] As the alkaline compound and the base generator contained in the rinsing liquid, the alkaline compounds that can be contained when the above-mentioned developer contains an organic solvent and the compounds exemplified as the base generator can be cited, and the preferred modes are the same.

[1053] Regarding the alkaline compound and the base generator contained in the rinsing liquid, it can be selected in consideration of solubility in the solvent in the rinsing liquid and the like.

[1054] When the rinsing liquid contains at least one of an alkaline compound and a base generator, the content of the alkaline compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinsing liquid. The lower limit of the above content is not particularly limited, and for example, it is preferably 0.1% by mass or more.

[1055] When the alkaline compound or the base generator is solid in the environment where the rinsing liquid is used, the content of the alkaline compound or the base generator is also preferably 70 to 100% by mass based on the total solid content of the rinsing liquid.

[1056] When the rinsing liquid contains at least one of an alkaline compound and a base generator, the rinsing liquid may contain only one kind of the alkaline compound and the base generator or may contain two or more kinds of the alkaline compound and the base generator. When at least one of the alkaline compound and the base generator is two or more kinds, it is preferably within the above range in total.

[1057] The rinsing liquid may further contain other components.

[1058] As other components, for example, well-known surfactants or well-known antifoaming agents can be cited.

[1059] 〔Method for supplying rinsing liquid〕

[1060] As long as a desired pattern can be formed, the method for supplying the rinsing liquid is not particularly limited, and there are the following methods: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate by liquid accumulation, a method of supplying the rinsing liquid to the substrate by spraying, and a method of continuously supplying the rinsing liquid to the substrate by means of a direct nozzle or the like.

[1061] From the viewpoints of the permeability of the rinsing liquid, the removability of the non-image portion, and the manufacturing efficiency, there is a method of supplying the rinsing liquid using a spray nozzle, a direct nozzle, a spray nozzle, etc., and a method of continuously supplying using a spray nozzle is preferred. From the viewpoint of the permeability of the rinsing liquid to the image portion, a method of supplying using a spray nozzle is more preferred. The type of the nozzle is not particularly limited, and a direct nozzle, a spray nozzle, a spray nozzle, etc. can be cited.

[1062] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the above-mentioned exposed film using a direct nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle.

[1063] As the method for supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially stationary state on the substrate, a step of vibrating the rinsing liquid on the substrate with ultrasonic waves or the like, and a step of combining them can be adopted.

[1064] As the rinsing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is more preferred. The temperature of the rinsing liquid during rinsing is not particularly limited, and 10 to 45 °C is preferred, and 18 °C to 30 °C is more preferred.

[1065] In the developing step, after treatment with a developer or after cleaning the pattern with a rinsing liquid, a step of bringing the treatment liquid into contact with the pattern can be included. Also, a method such as supplying the treatment liquid before the developer or rinsing liquid in contact with the pattern is completely dried can be adopted.

[1066] As the above-mentioned treatment liquid, a treatment liquid containing at least one of water and an organic solvent and at least one of an alkaline compound and a base generator can be cited.

[1067] The preferred modes of the above-mentioned organic solvent, and at least one of the alkaline compound and the base generator are the same as the preferred modes of at least one of the organic solvent, and the alkaline compound and the base generator used in the above-mentioned rinsing liquid.

[1068] The method of supplying the treatment liquid to the pattern can use the same method as the method of supplying the above-mentioned rinsing liquid, and the preferred mode is also the same.

[1069] The content of the basic compound or the base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example.

[1070] Moreover, when the basic compound or the base generator is solid in the environment where the treatment liquid is used, the content of the basic compound or the base generator is also preferably 70 to 100% by mass relative to the total solid components of the treatment liquid.

[1071] When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one of the basic compound and the base generator, or may contain two or more of the basic compound and the base generator. When at least one of the basic compound and the base generator is two or more, it is preferable that the total is within the above range.

[1072] <Heating step>

[1073] The pattern obtained through the development step (the pattern after rinsing in the case where a rinsing step is performed) can be subjected to a heating step of heating the pattern obtained through the above development.

[1074] That is, the method for manufacturing a cured product of the present invention may include a heating step of heating the pattern obtained through the development step.

[1075] Moreover, the method for manufacturing a cured product of the present invention may also include a heating step of heating a pattern obtained by other methods without performing the development step or a film obtained through a film formation step.

[1076] In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as polyimide.

[1077] Moreover, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin is also performed.

[1078] As the heating temperature (the maximum heating temperature) in the heating step, 50 to 450°C is preferable, 150 to 350°C is more preferable, 150 to 250°C is further preferable, 160 to 250°C is still more preferable, and 160 to 230°C is particularly preferable.

[1079] The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the above pattern by heating and using the action of an alkali or the like generated from the above base generator.

[1080] In the heating process, heating is preferably carried out at a heating rate of 1 to 12 °C per minute from the temperature at the start of heating to the maximum heating temperature. The above heating rate is more preferably 2 to 10 °C per minute, and further preferably 3 to 10 °C per minute. By setting the heating rate to 1 °C per minute or more, productivity can be ensured and excessive volatilization of acid or solvent can be prevented. By setting the heating rate to 12 °C per minute or less, the residual stress of the cured product can be alleviated.

[1081] In addition, in the case of an oven capable of rapid heating, from the temperature at the start of heating to the maximum heating temperature, it is preferably carried out at a heating rate of 1 to 8 °C per second, more preferably 2 to 7 °C per second, and further preferably 3 to 6 °C per second.

[1082] 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, in the case of drying after applying the resin composition of the present invention to a substrate, it is the temperature of the dried film (layer). For example, it is preferably heated starting from a temperature 30 to 200 °C lower than the boiling point of the solvent contained in the resin composition.

[1083] 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.

[1084] In particular, in the case of forming a multi-layer laminate, from the viewpoint of interlayer adhesion, 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.

[1085] The upper limit of the above heating temperature is preferably 350 °C or lower, more preferably 250 °C or lower, and further preferably 240 °C or lower.

[1086] Heating can be carried out in stages. As an example, the following process can be carried out: heating from 25 °C to 120 °C at 3 °C per minute and holding at 120 °C for 60 minutes, heating from 120 °C to 180 °C at 2 °C per minute and holding at 180 °C for 120 minutes. And, as described in the specification of U.S. Patent No. 9,159,547, it is also preferable to carry out the treatment while irradiating ultraviolet rays. The characteristics of the film can be improved through this pretreatment process. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be a process with two or more stages. For example, the first-stage pretreatment process can be carried out in the range of 100 to 150 °C, and then the second-stage pretreatment process can be carried out in the range of 150 to 200 °C.

[1087] Furthermore, cooling can be performed after heating, and the cooling rate at this time is preferably 1 to 5 °C per minute.

[1088] Regarding the heating process, from the viewpoint of preventing the decomposition of specific resins, it is preferably carried out in an environment with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon and performing the process under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[1089] The heating mechanism in the heating process is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven, etc.

[1090] <Post-development exposure process>

[1091] The pattern obtained through the development process (in the case of performing a rinsing process, it is the rinsed pattern) can also be used in place of or in addition to the above heating process for the post-development exposure process of exposing the pattern after the development process.

[1092] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure process of exposing the pattern obtained through the development process. The method for manufacturing the cured product of the present invention may include a heating process and a post-development exposure process, or may include either the heating process or the post-development exposure process.

[1093] In the post-development exposure process, for example, it can promote reactions such as the cyclization of polyimide precursors, etc. through the photosensitivity of photo-base generators, and the reaction of the detachment of acid-decomposable groups through the photosensitivity of photo-acid generators.

[1094] In the post-development exposure process, as long as at least a part of the pattern obtained in the development process is exposed, but it is preferably that the above pattern is entirely exposed.

[1095] In terms of the exposure energy conversion at the wavelength at which the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 .

[1096] Regarding the post-development exposure process, for example, it can be performed using the light source in the above exposure process, and it is preferably to use broadband light.

[1097] <Metal layer formation process>

[1098] The pattern obtained through the development process (preferably the pattern used in at least one of the heating process and the post-development exposure process) can also be used in the metal layer formation process of forming a metal layer on the pattern.

[1099] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained through a developing step (preferably a pattern subjected to at least one of a heating step and a post-development exposure step).

[1100] The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

[1101] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US 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 methods combining these can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be cited. As a preferred method of plating, electroplating using a copper sulfate plating solution or a copper cyanide plating solution can be cited.

[1102] The thickness of the metal layer, measured at the thickest part, is preferably 0.01 to 50 μm, more preferably 1 to 10 μm.

[1103] <Use>

[1104] As fields where the method for manufacturing the cured product of the present invention or the cured product of the present invention can be applied, insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. can be cited. In addition, sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or cases where patterns are formed on insulating films for mounting applications such as the above by etching can be cited. Regarding these uses, for example, reference can be made to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide", April 2008, Masaki Kakinuma / supervised, CMC Technical Library "Fundamentals and Development of Polyimide Materials", published in November 2011, Japan Polyimide & Aromatic Polymer Research Group / edited "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc.

[1105] The method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used for the manufacture of printing plates such as offset printing plates or screen printing plates, the use for etching of molded parts, the manufacture of protective paints and dielectric layers in electronics, especially microelectronics, etc.

[1106] (Laminated body and method for manufacturing laminated body)

[1107] The laminated body of the present invention refers to a structure having multiple layers composed of the cured product of the present invention.

[1108] The laminated body is a laminated body including two or more layers composed of a cured product, and may also be a laminated body formed by laminating three or more layers.

[1109] Among the two or more layers composed of the above-mentioned cured product contained in the above-mentioned laminated body, at least one layer is a layer composed of the cured product of the present invention. From the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the above shrinkage, etc., it is also preferable that all the layers composed of the cured product contained in the above-mentioned laminated body are composed of the cured product of the present invention.

[1110] That is, the method for manufacturing the laminated body of the present invention preferably includes the method for manufacturing the cured product of the present invention, and more preferably includes the step of repeating the method for manufacturing the cured product of the present invention multiple times.

[1111] The laminated body of the present invention preferably includes two or more layers composed of a cured product, and is in a manner that includes a metal layer between any of the layers composed of the above-mentioned cured product. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step.

[1112] That is, the method for manufacturing the laminated body of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer composed of the cured product between multiple manufacturing methods of the cured product. The preferred manner of the metal layer forming step is as described above.

[1113] As the above-mentioned laminated body, for example, a laminated body having a layer structure including at least three layers of a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product laminated in sequence can be cited as a preferred laminated body.

[1114] The layer composed of the first cured product and the layer composed of the second cured product are preferably both layers composed of the cured product of the present invention. The resin composition of the present invention for forming the layer composed of the first cured product and the resin composition of the present invention for forming the layer composed of the second cured product may be a composition with the same composition or a composition with different compositions. The metal layer in the laminated body of the present invention can preferably be used as a metal wiring such as a rewiring layer.

[1115] <Laminating step>

[1116] The method for manufacturing the laminated body of the present invention preferably includes a laminating step.

[1117] The lamination process is a series of processes including at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, (d) a heating process, and a post-development exposure process in sequence on the surface of a pattern (resin layer) or a metal layer. Among them, it can be in a manner of repeating at least one of (a) the film formation process, (d) the heating process, and the post-development exposure process. And, it can include (e) a metal layer formation process after at least one of (d) the heating process and the post-development exposure process. In the lamination process, it is of course possible to appropriately further include the above-mentioned drying process and the like.

[1118] When further performing the lamination process after the lamination process, the surface activation treatment process can be further performed after the above-mentioned exposure process and after the above-mentioned heating process or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment is exemplified. The details of the surface activation treatment will be described later.

[1119] The above-mentioned lamination process is preferably performed 2 to 20 times, more preferably 2 to 9 times.

[1120] For example, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, it is preferably a structure in which the resin layer is 2 or more layers and 20 or less layers, and more preferably 2 or more layers and 9 or less layers.

[1121] The composition, shape, film thickness, etc. of each of the above layers can be the same or different.

[1122] In the present invention, it is particularly preferable to further form a cured product (resin layer) of the above-mentioned resin composition of the present invention in a manner of covering the above-mentioned metal layer after providing the metal layer. Specifically, it can be exemplified by a manner of repeating in the order of (a) a film formation process, (b) an exposure process, (c) a development process, (d) a heating process, at least one of the post-development exposure process, and (e) a metal layer formation process, or a manner of repeating in the order of (a) a film formation process, at least one of (d) a heating process and the post-development exposure process, and (e) a metal layer formation process. By alternately performing the lamination process of the resin composition layer (resin layer) of the present invention and the metal layer formation process, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[1123] (Surface activation treatment process)

[1124] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment process of performing surface activation treatment on at least a part of the above-mentioned metal layer and resin composition layer.

[1125] The surface activation treatment step is usually carried out after the metal layer formation step, but it can also be carried out after the above-mentioned development step (preferably after at least one of the heating step and the post-exposure baking step), and the metal layer formation step can be carried out after the surface activation treatment step of the resin composition layer.

[1126] The surface activation treatment can be carried out only on at least a part of the metal layer, or only on at least a part of the exposed resin composition layer, or on at least a part of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably carried out on at least a part of the metal layer, and preferably on a part or all of the area of the metal layer where the resin composition layer is formed on the surface. Thus, by carrying out the surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on its surface can be improved.

[1127] The surface activation treatment is also preferably carried out on a part or all of the exposed resin composition layer (resin layer). Thus, by carrying out the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer and the resin layer provided on the surface-activated surface can be improved. In particular, in the case of negative development or the like where the resin composition layer is cured, it is not easily damaged by the surface treatment, and the adhesion can be easily improved.

[1128] The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated into the present specification.

[1129] (Semiconductor device and method for manufacturing the same)

[1130] The present invention also discloses a semiconductor device including the cured product or laminate of the present invention.

[1131] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing the cured product or the method for manufacturing the laminate of the present invention.

[1132] As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for rewiring, reference can be made to the description in paragraphs 0213 to 0218 and the description of FIG. 1 in Japanese Patent Laid-Open No. 2016-027357, and these contents are incorporated into the present specification.

[1133] Examples

[1134] Hereinafter, the present invention will be further specifically described with reference to examples. The materials, amounts used, ratios, treatment contents, treatment sequences, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[1135] <Synthesis of Resin>

[1136] [Synthesis Example A-1: Synthesis of Polyimide Precursor (A-1)]

[1137] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme were mixed and stirred at 60 °C for 10 hours. Further, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 °C, and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at -10 ± 4 °C. 2 During the addition of SOCl 1 , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0 °C over 20 minutes. Next, after reacting the reaction mixture at 0 °C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure at 45 °C for 3 days to obtain a polyimide precursor (A-1). The weight-average molecular weight of this polyimide precursor (A-1) was 19,000. By

[1138] [Chemical Formula 70]

[1139]

[1140] [Synthesis Example A-2: Synthesis of Polyimide Precursor (A-2)]

[1141] 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed (water content: 88 ppm), and the mixture was stirred at 60 °C for 10 hours. Further, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl 2 The obtained diester was converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-1, and a polyimide precursor (A-2) was obtained in the same manner as in Synthesis Example A-1. The weight-average molecular weight of this polyimide precursor (A-2) was 20,000. By 1 1H-NMR, it was confirmed that the obtained polyimide precursor (A-2) contained a repeating unit represented by the following formula (A-2).

[1142] [Chemical formula 71]

[1143]

[1144] [Synthesis Example A-3: Synthesis of polyimide precursor (A-3)]

[1145] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diethylene glycol dimethyl ether were mixed, and the mixture was stirred at 60 °C for 10 hours. Further, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of 4,4'-oxybisphthalic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl 2 The obtained diester was converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-1, and a polyimide precursor (A-3) was obtained in the same manner as in Synthesis Example A-1. The weight-average molecular weight of this polyimide precursor (A-3) was 18,000. By 1 1H-NMR, it was confirmed that the obtained polyimide precursor (A-3) contained a repeating unit represented by the following formula (A-3).

[1146] [Chemical formula 72]

[1147]

[1148] [Synthesis Example A-4: Synthesis of Polyimide Precursor (A-4)]

[1149] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed (water content 67 ppm), and stirred at 60 °C for 10 hours. Further, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to prepare a diester of 4,4'-oxybisphthalic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl 2 and converting it to a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-1, a polyimide precursor (A-4) was obtained in the same manner as in Synthesis Example A-1. The weight-average molecular weight of this polyimide precursor (A-4) was 19,000. By 1 1H-NMR, it was confirmed that the obtained polyimide precursor (A-4) contained a repeating unit represented by the following formula (A-4).

[1150] [Chemical Formula 73]

[1151]

[1152] [Synthesis Example A-5: Synthesis of Polyimide Precursor (A-5)]

[1153] 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed (water content 88 ppm), and stirred at 60 °C for 10 hours. Further, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to prepare a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl 2 and converting it to a polyimide precursor with 2,2-bis[4-(4-aminophenoxy)phenyl]propane in the same manner as in Synthesis Example A-1, a polyimide precursor (A-5) was obtained in the same manner as in Synthesis Example A-1. The weight-average molecular weight of this polyimide precursor (A-5) was 23,000. By 1By \(^1\)H-NMR, it was confirmed that the obtained polyimide precursor (A-5) contained a repeating unit represented by the following formula (A-5).

[1154] [Chemical formula 74]

[1155]

[1156] [Synthesis Example A-6: Synthesis of polyimide precursor (A-6)]

[1157] 10.4 g (47.6 mmol) of pyromellitic dianhydride, 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 5 hours to prepare a diester of pyromellitic dianhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. Then, after cooling the mixture to -20 °C, 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes, and the mixture was stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride.

[1158] Then, a solution prepared by dissolving 19.7 g (61.8 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. Then, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Then, the polyimide precursor was precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was filtered, stirred in 4 L of water for 30 minutes again, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 °C for 2 days to obtain a polyimide precursor (A-6). The weight-average molecular weight of the obtained polyimide precursor (A-6) was 26,500. By 1 \(^1\)H-NMR, it was confirmed that the obtained polyimide precursor (A-6) contained a repeating unit represented by the following formula (A-6).

[1159] [Chemical formula 75]

[1160]

[1161] [Synthesis Example CA-1: Synthesis of polyimide precursor (CA-1)]

[1162] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride, 14.22 g (131.58 mmol) of benzyl alcohol, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 0 °C for 1 hour, and then stirred at 60 °C for 3 hours to produce an adduct of 4,4'-oxybisphthalic acid and benzyl alcohol. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10 °C, and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at -10 ± 4 °C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0 °C over 20 minutes. Then, after allowing the reaction mixture to react at 0 °C for 1 hour, 70 g of ethanol was added and the mixture was stirred at room temperature overnight. Then, the polyimide precursor was precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes.

[1163] The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 °C for 3 days. The weight-average molecular weight of this polyimide precursor was 18,000.

[1164] By 1 1H-NMR, it was confirmed that the obtained polyimide precursor (CA-1) contained the repeating unit represented by the following formula (CA-1).

[1165] [Chemical formula 76]

[1166]

[1167] [Synthesis Example PI-1: Synthesis of Cyclized Polyimide (PI-1)]

[1168] In a flask equipped with a condenser and a stirrer, while removing moisture, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100.0 g of N-methylpyrrolidone (NMP). Then, 11.9 g (45 mmol) of the following diamine (AA-1) was added, and the mixture was stirred at 25 °C for 3 hours and further stirred at 45 °C for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 °C for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added for dilution.

[1169] The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was removed by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried under reduced pressure at 40 °C for 1 day to obtain polyimide (PI-1). The molecular weight of polyimide (PI-1) was Mw = 19,000.

[1170] By 1 1H-NMR, it was confirmed that the structure of polyimide (PI-1) was the structure represented by the following formula (PI-1).

[1171] [Chemical formula 77]

[1172]

[1173] [Synthesis example AA-1: Synthesis of diamine (AA-1)]

[1174] In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate and cooled to 5°C ...

Claims

1. A resin composition, comprising: At least one resin selected from polyimide and a polyimide precursor having a polymerizable group; and Compound B1 represented by the following formula (1-1), The ethylenic unsaturated bond valence of the compound B1 is 3.0 mmol / g or more, In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar 1 each independently represents an optionally substituted aromatic group, Z represents a hydrogen atom or an n-valent organic group, and Z does not contain -X 1 -C(=O)-C(=O)-X 2 - such a structure, X 1 and X 2 each independently represents -O- or -NH-, n represents an integer of 1 to 6, m represents 1 or 2. When n is 1, m is 2 and Z is a hydrogen atom. When n is an integer of 2 to 6, Z represents an n-valent organic group, and Z and Ar 1 have a structure without an ethylenic unsaturated bond.

2. The resin composition according to claim 1, Wherein, R in formula (1-1) 1 is a hydrogen atom and Ar 1 is an optionally substituted aromatic hydrocarbon group.

3. The resin composition according to claim 1 or 2, which contains two or more kinds of compound B1, or contains compound B1 and a polymerizable compound different from compound B1.

4. The resin composition according to claim 1 or 2, Wherein, The molecular weight of the compound B1 is 2000 or less.

5. A resin composition, comprising: At least one resin selected from polyimide and a polyimide precursor having a polymerizable group; and Compound B2 represented by the following formula (1-2), In formula (1-2), L 1 ~L 3 each independently represents a divalent linking group having no aromatic ring structure, and R a each independently represents a hydrogen atom or a monovalent organic group.

6. The resin composition according to any one of claims 1, 2 and 5, which further contains an azole compound.

7. The resin composition according to any one of claims 1, 2 and 5, which is used for forming an interlayer insulating film for a rewiring layer.

8. A cured product, which is obtained by curing the resin composition according to any one of claims 1, 2 and 5.

9. A laminate, which comprises two or more layers composed of the cured product according to claim 8, and a metal layer is included between any two layers composed of the cured product.

10. A method for manufacturing a cured product, which includes a film forming step of applying the resin composition according to any one of claims 1, 2 and 5 on a substrate to form a film.

11. The method for manufacturing a cured product according to claim 10, which Includes: An exposure step of selectively exposing the film; And A developing step of developing the film with a developer to form a pattern.

12. The method for manufacturing a cured product according to claim 10, which includes a heating step of heating the film.

13. A method for manufacturing a laminate, which includes the method for manufacturing a cured product according to claim 10.

14. A method for manufacturing a semiconductor device, which includes the method for manufacturing a cured product according to claim 10.

15. A semiconductor device, which contains the cured product according to claim 8.

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