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

Abstract

The present invention provides a resin composition containing a resin and a base generator represented by the following formula (1-1), a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a semiconductor device containing the cured product or the laminate, and a base generator. #imgabs0#

Description

Technical Field

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

[0002] Cyclized resins such as polyimide are excellent in heat resistance, insulation, etc., and thus can be used for various applications. The above applications are not particularly limited. Taking a semiconductor device for mounting as an example, examples include use as a material for an insulating film, a sealing material, or a protective film. Further, it can also be used as a base film, a cover film, etc. of a flexible substrate.

[0003] For example, in the above applications, cyclized resins such as polyimide are used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

[0004] For example, such a resin composition is applied to a substrate by coating or the like 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.

[0005] Precursors of the above cyclized resins such as polyimide precursors are cyclized by heating, for example, and become cyclized resins such as polyimide in the cured product.

[0006] The resin composition can be applied by a known coating method or the like. Therefore, for example, the design freedom regarding the shape, size, application position, etc. at the time of applying the resin composition to be applied is high, and it can be said that the adaptability in manufacturing is excellent. Considering from the viewpoint that such adaptability in manufacturing is excellent in addition to the high performance of cyclized resins such as polyimide, the industrial application expansion of the above resin composition is increasingly expected.

[0007] For example, Patent Document 1 describes a photosensitive resin composition having a polymer precursor that promotes the reaction for generating a final product by an alkaline substance or by heating in the presence of an alkaline substance and a specific structure, and containing an alkali generator that generates an alkali by irradiation with electromagnetic waves and heating.

[0008] Patent Document 2 describes a resin composition containing the following components (a) to (d).

[0009] (a) A polyimide precursor having a specific structural unit

[0010] (b) A compound that generates free radicals by irradiation with actinic rays

[0011] (c) A compound having a specific structure

[0012] (d) A solvent

[0013] Prior Art Documents

[0014] Patent document

[0015] Patent document 1: Japanese Patent Application Laid-Open No. 2011-121962

[0016] Patent document 2: Japanese Patent Application Laid-Open No. 2014-201695 Summary of the invention

[0017] Technical problem to be solved by the invention

[0018] In a resin composition for obtaining a cured product, it is required that the obtained cured product has excellent chemical resistance.

[0019] An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent chemical resistance, 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 semiconductor device containing the above cured product or the above laminate, and a novel base generator.

[0020] Means for solving the technical problem

[0021] Examples of representative embodiments of the present invention are shown below.

[0022] <1>A resin composition comprising a resin and a base generator represented by the following formula (1-1),

[0023] [Chemical formula 1]

[0024]

[0025] In formula (1-1), each R is independently a hydrogen atom or a monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs may be linked to form a ring structure. OH described in formula (1-1) represents a hydroxyl group, L is a divalent organic group, and has at least one heteroatom on the linking chain of the shortest path connecting an adjacent oxygen atom and a carbon atom.

[0026] <2>The resin composition according to <1>, wherein

[0027] The heteroatom present on the linking chain of the shortest path contained in L of formula (1-1) is any one of a nitrogen atom, an oxygen atom, or a sulfur atom.

[0028] <3>The resin composition according to <1> or <2>, which contains a compound represented by the following formula (1-2) as the above base generator.

[0029] [Chemical formula 2]

[0030]

[0031] In formula (1-2), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs may be linked to form a ring structure, and L 1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NR N -, and R N represents a hydrogen atom or a monovalent organic group, and R 1 and R 2 each independently represent a hydrogen atom or an organic group. At least two of the two Rs 1 and R 2 may combine to form a ring structure. The bond with a dashed line represents a single bond or a double bond. n represents 0 or 1. When the bond with a dashed line is a double bond, n is 1; when the bond with a dashed line is a single bond, n is 0.

[0032] <4>The resin composition according to any one of <1> to <3> above contains a compound represented by the following formula (1-3) as the above-mentioned base generator.

[0033] [Chemical formula 3]

[0034]

[0035] In formula (1-3), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs may be linked to form a ring structure, and L 1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NR N -, and R N represents a hydrogen atom or a monovalent organic group, and R 3 are each independently a hydrogen atom or a monovalent organic group, and R 3 in which at least two may be linked to form a ring structure.

[0036] <5>The resin composition according to any one of <1> to <4> above contains a compound represented by the following formula (1-4) as the above-mentioned base generator.

[0037] [Chemical formula 4]

[0038]

[0039] In formula (1-4), R 2 and R 4 each independently represent a monovalent organic group. The two Rs 2 with each other or R 2 and R 4 may be linked to form a ring structure, and L 1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NRN -, R N represents a hydrogen atom or a monovalent organic group, and R 3 each independently represents a hydrogen atom or a monovalent organic group, and at least two of the Rs 3 may be linked to form a ring structure.

[0040] <6>The resin composition according to any one of <1> to <5>, wherein

[0041] the resin is a precursor of a cyclized resin.

[0042] <7>The resin composition according to any one of <1> to <6> further comprises a photoinitiator.

[0043] <8>The resin composition according to any one of <1> to <7> further comprises a polymerizable compound.

[0044] <9>The resin composition according to any one of <1> to <8> is used for forming an interlayer insulating film for a rewiring layer.

[0045] <10>A cured product which is cured from the resin composition according to any one of <1> to <9>.

[0046] <11>A laminate comprising two or more layers made of the cured product described in <10>, and a metal layer is included between any two layers made of the above cured product.

[0047] <12>A method for manufacturing a cured product, the method including a film forming step of applying the resin composition according to any one of <1> to <9> on a substrate to form a film.

[0048] <13>The method for manufacturing a cured product according to <12>, the method including:

[0049] an exposure step of selectively exposing the above film; and

[0050] a developing step of developing the above film with a developer to form a pattern.

[0051] <14>The method for manufacturing a cured product according to <12> or <13> includes a heating step of heating the above film at 50 to 450 °C.

[0052] <15>A semiconductor device comprising the cured product described in <10> or the laminate described in <11>.

[0053] <16>A base generator represented by the following formula (1-1),

[0054] [Chemical formula 5]

[0055]

[0056] In formula (1-1), each R is independently a hydrogen atom or a monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs can be linked to form a ring structure. The OH described in formula (1-1) represents a hydroxyl group, L is a divalent organic group, and there is at least one heteroatom on the linking chain of the shortest path connecting adjacent oxygen and carbon atoms.

[0057] <17>The base generator according to <16> is represented by the following formula (1-2),

[0058] [Chemical formula 6]

[0059]

[0060] In formula (1-2), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs can be linked to form a ring structure, L 1 represents an alkylene group which may be substituted, Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, R 1 and R 2 each independently represent a hydrogen atom or an organic group, and at least two of the two Rs 1 and R 2 can combine to form a ring structure. The bond with the dashed part represents a single bond or a double bond, n represents 0 or 1. When the bond with the dashed part is a double bond, n is 1; when the bond with the dashed part is a single bond, n is 0.

[0061] <18>The base generator according to <16> or <17> is represented by the following formula (1-3),

[0062] [Chemical formula 7]

[0063]

[0064] In formula (1-3), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs can be linked to form a ring structure, L 1 represents an alkylene group which may be substituted, Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, R 3 are each independently a hydrogen atom or a monovalent organic group, and at least two of the Rs 3 can be linked to form a ring structure.

[0065] <19>The base generator according to any one of <16> to <18> is represented by the following formula (1-4):

[0066] [Chemical formula 8]

[0067]

[0068] In formula (1-4), R 2 and R 4 each independently represents a monovalent organic group, and two Rs 2 with each other or R 2 and R 4 may be linked to form a ring structure, L 1 represents an alkylene group which may be substituted, Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, R 3 each independently is a hydrogen atom or a monovalent organic group, and at least two of Rs 3 may be linked to form a ring structure.

[0069] Advantages of the Invention

[0070] According to the present invention, there are provided a resin composition capable of obtaining a cured product having excellent chemical resistance, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a semiconductor device including the cured product or the laminate, and a novel base generator. Detailed Embodiments

[0071] Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments.

[0072] In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as a lower limit value and an upper limit value, respectively.

[0073] In this specification, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved.

[0074] In the notation of groups (atomic groups) in this specification, those not marked with substituted and unsubstituted marks include groups (atomic groups) having no substituents as well as groups (atomic groups) having substituents. For example, "alkyl" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).

[0075] 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. Moreover, as the light used for exposure, there can be cited bright line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiations.

[0076] In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic acid" means either or both of "acrylic acid" and "methacrylic acid", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl".

[0077] In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0078] In this specification, the total solid content means the total mass of the components other than the solvent among all the components of the composition. Moreover, in this specification, the solid content concentration is the mass percentage of the components other than the solvent with respect to the total mass of the composition.

[0079] 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, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and serially using the guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all of the above are manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. Among them, when the solubility is low or the like and THF is not suitable as the eluent, NMP (N-methyl-2-pyrrolidone) can also be used. Moreover, unless otherwise specified, UV ray (ultraviolet ray) detectors with a wavelength of 254 nm are used for detection in GPC measurement.

[0080] 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 on the upper side or the lower side of the layer serving as the reference among the plurality of 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. Moreover, unless otherwise specified, the direction in which the base material layer is stacked is referred to as "upper", or when there is a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". In addition, these upper and lower directions are set for convenience in this specification. In an actual manner, the "upper" direction in this specification may be different from the vertically upward direction.

[0081] In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. Moreover, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component.

[0082] 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.

[0083] In this specification, a combination of preferred modes is a more preferred mode.

[0084] (Resin composition)

[0085] The resin composition of the present invention contains a resin and a base generating agent represented by the following formula (1-1) (hereinafter, also referred to as "specific base generating agent").

[0086] [Chemical formula 9]

[0087]

[0088] In formula (1-1), each R is independently a hydrogen atom or a monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs may be linked to form a ring structure. L is a divalent organic group and has at least one heteroatom on the linking chain of the shortest path connecting the adjacent oxygen atom and carbon atom.

[0089] The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and more preferably for forming a photosensitive film for exposure and development using a developer containing an organic solvent.

[0090] The resin composition of the present invention can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer.

[0091] Moreover, the resin composition of the present invention can be used to form a positive-tone developing photosensitive film, and can also be used to form a negative-tone developing photosensitive film.

[0092] In the present invention, negative-tone development refers to development in which the non-exposed portion is removed by development during exposure and development, and positive-tone development refers to development in which the exposed portion is removed by development.

[0093] As the above-described exposure method, the above-described developer, and the above-described development method, for example, the exposure method described in the exposure step in the manufacturing method of the cured product described later, the developer and the development method described in the development step can be used.

[0094] According to the resin composition of the present invention, a cured film having excellent chemical resistance can be obtained.

[0095] The mechanism by which the above effects can be obtained is not yet clear, but it is presumed as follows.

[0096] Hitherto, resin compositions containing resins and base generators have been used in various fields.

[0097] For example, a composition containing a precursor of a cyclized resin such as a polyimide precursor and a base generator is heated or the like to generate a base from the base generator, whereby a cured product containing a polyimide resin can be obtained.

[0098] Moreover, a composition containing a polymerizable compound having an epoxy group and a base generator can also be used, and the composition is heated or the like to generate a base from the base generator, whereby the polymerizable compound having an epoxy group is cured to obtain a cured product.

[0099] Here, as a result of research by the present inventors, it has been found that when a conventional base generator is used, the chemical resistance is poor.

[0100] It is presumed that this is because the structure of the base generator itself has low polarity and high solubility in an organic solvent.

[0101] The base generator represented by the formula (1-1) used in the present invention has at least one or more heteroatoms on the linking chain of the shortest path connecting adjacent oxygen atoms and carbon atoms. It is presumed that as a result, the polarity of the base generator becomes higher, and the decomposition product or unreacted base generator of the base generator becomes less soluble in the organic solvent, thereby improving the chemical resistance of the film obtained from the resin composition. By improving the chemical resistance, there are advantages such as, for example, when another resin composition is further applied to the formed cured product to form a pattern, etc., suppressing the dissolution of the cured product in the solvent contained in the other resin composition.

[0102] Furthermore, it is considered that by having a heteroatom as described above, the mobility of the linking chain is improved, and when a specific base generator is used as the base generator, the base generation efficiency is easily improved.

[0103] In particular, it is considered that when a precursor of a cyclized resin is used as the resin, the alkali generation efficiency is improved, and the elongation at break of the obtained cured film is also improved.

[0104] Furthermore, it is considered that by including a heteroatom in a specific alkali generator, the surface free energy of the molecule is increased. Accordingly, it is considered that the alkali generator, which is originally likely to be biased toward a side different from the substrate side of the film, is distributed in a more uniform state in the depth direction of the film, and thus the generated alkali is also likely to be uniformly distributed in the film.

[0105] It is considered as follows: When a precursor of a cyclized resin is used, if the alkali generator is biased toward the film surface, cyclization is likely to occur near the surface on the side opposite to the substrate side of the film, and cyclization is less likely to occur near the substrate side (i.e., the deep side of the film) of the film. Here, when the precursor of the cyclized resin cyclizes, film shrinkage occurs. Film shrinkage means that the volume of the cured product (e.g., cured film) obtained after curing is reduced (shrunk) compared to the composition before curing (e.g., composition film before heating). For example, as described above, when cyclization is likely to occur near the surface on the side opposite to the substrate side of the film and cyclization is less likely to occur near the substrate of the film, film shrinkage is likely to occur on the side opposite to the substrate side of the film, and the shape of the obtained cured product may sometimes be a positive conical shape.

[0106] As described above, it is considered that the specific alkali generator used in the present invention is likely to be distributed in a more uniform state in the depth direction of the film. Accordingly, it is considered that in the present invention, the structures showing the property of generating alkali are distributed in an approximately uniform state throughout the film, and thus differences in film shrinkage degree caused by position are less likely to occur, and the rectangularity of the pattern is improved.

[0107] Here, the specific alkali generator is not described in Patent Documents 1 and 2.

[0108] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0109] <Resin>

[0110] The resin composition of the present invention contains a resin.

[0111] The resin is not particularly limited, and examples thereof include resins used in conventional pattern-forming compositions. Preferably, it contains at least one resin (specific resin) selected from cyclized resins and their precursors, and more preferably contains a precursor of a cyclized resin.

[0112] The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0113] In the present invention, the main chain means the relatively longest bonding chain in the resin molecule.

[0114] Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like.

[0115] The precursor of the cyclized resin refers to a resin whose chemical structure changes by external stimuli to become a cyclized resin. Preferably, it is a resin whose chemical structure changes by heat to become a cyclized resin. More preferably, it is a resin that forms a ring structure by a ring-closing reaction due to heat to become a cyclized resin.

[0116] Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, and the like.

[0117] That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as a specific resin.

[0118] The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.

[0119] Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0120] When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, and more preferably contains a radical polymerization initiator described below and a radical crosslinking agent described below. A sensitizer described below can be further contained as needed. A negative photosensitive film is formed from such a resin composition of the present invention, for example.

[0121] Moreover, the specific resin may have a polarity-converting group such as an acid-decomposable group.

[0122] When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described below. For example, a positive photosensitive film or a negative photosensitive film as a chemically amplified type is formed from such a resin composition of the present invention.

[0123] 〔Polyimide Precursor〕

[0124] The polyimide precursor used in the present invention is not particularly limited in terms of its type, etc., but preferably contains a repeating unit represented by the following formula (2).

[0125] [Chemical Formula 10]

[0126]

[0127] In formula (2), A 1 and A 2 each independently represent an oxygen atom or -NH-, and R 111 represents a divalent organic group, R115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0128] A in formula (2) 1 and A 2 each independently represents an oxygen atom or -NH-, preferably an oxygen atom.

[0129] R in formula (2) 111 represents a divalent organic group. As the divalent organic group, groups containing a linear or branched aliphatic group, a cycloaliphatic group, and an aromatic group can be exemplified. Preferably, 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 of these is more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group can be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the cycloaliphatic group and the aromatic group can be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and particularly preferably a group represented by -Ar-L-Ar-. Among them, Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted with a fluorine atom, -0-, -CO-, -S-, -SO2-, 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.

[0130] R 111 is preferably derived from diamine. As the diamine used in the production of the polyimide precursor, linear or branched aliphatic, cycloaliphatic, or aromatic diamines can be cited. Only one kind of diamine can be used, or two or more kinds can be used.

[0131] Specifically, a diamine containing 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 of these is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. The hydrocarbon group in the chain of the linear or branched aliphatic group can be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the cycloaliphatic group and the aromatic group can be substituted with a group containing a heteroatom. Examples of the group containing an aromatic group include the following groups.

[0132] [Chemical formula 11]

[0133]

[0134] In the formula, A represents a single bond or a divalent 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-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination 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-, -C(=O)-, -S- or -SO2-, and further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0135] In the formula, * represents a bonding site with other structures.

[0136] As the diamine, specifically, those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(2-aminophenoxy)phenyl] sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-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,At least one diamine selected from 5-dimethyl-p-phenylenediamine, acetylguanamine, 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, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-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'-hexafluorobiphenyltoluene and 4,4'-diaminotetraphenyl.

[0137] Moreover, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferably used.

[0138] 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.

[0139] From the viewpoint of the flexibility of the obtained organic film, R is preferably 111 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-, -SO2- 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 -SO2-. The aliphatic hydrocarbon group herein is preferably an alkylene group.

[0140] Moreover, from the viewpoint of i-ray transmittance, R is preferably 111 a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[0141] Formula (51)

[0142] [Chemical formula 12]

[0143]

[0144] 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 a bonding site to the nitrogen atom in formula (2).

[0145] 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.

[0146] [Chemical formula 13]

[0147]

[0148] 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 a bonding site to the nitrogen atom in formula (2).

[0149] As the diamine that imparts the structure of formula (51) or (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.

[0150] R 115 in formula (2) 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.

[0151] In formula (5) or formula (6), * each independently represents a bonding site to other structures.

[0152] [Chemical formula 14]

[0153]

[0154] 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 with fluorine atoms, -O-, -CO-, -S-, -SO2-, and -NHCO-, and combinations thereof, more preferably a single bond, a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, and -SO2-, and still more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0155] Specifically, R 115 may be, for example, a tetracarboxylic acid residue remaining after removing the acid anhydride group from a tetracarboxylic dianhydride. 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 thereof.

[0156] The tetracarboxylic dianhydride is preferably represented by the following formula (0).

[0157] [Chemical formula 15]

[0158]

[0159] In formula (O), R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (2), and the preferred ranges are also the same.

[0160] As specific examples of the tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone 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'-oxybisphthalic 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 C1-C6 alkyl and C1-C6 alkoxy derivatives thereof may be mentioned.

[0161] Moreover, as a preferred example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 may also be mentioned.

[0162] In formula (2), R 111 and R 115 may each independently have at least one OH group. More specifically, as R 111， a residue of a diaminophenol derivative may be mentioned.

[0163] R in formula (2) 113 and R 114 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 includes a polymerizable group, and more preferably both include a polymerizable group. It is also preferred that at least one of R 113 and R 114At least one of them contains two or more polymerizable groups. As the polymerizable group, it is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy group, oxetanyl, benzoxazolyl, blocked isocyanate group, and amino group. As the free radical polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.

[0164] As the group having an ethylenically unsaturated bond, vinyl, allyl, isopropyl, 2-methylallyl, a group having an aromatic ring directly bonded to vinyl (for example, vinylphenyl, etc.), (meth)acrylamide group, (meth)acryloyloxy group, a group represented by the following formula (III), etc. can be cited, and a group represented by the following formula (III) is preferred.

[0165] [Chemical formula 16]

[0166]

[0167] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl, or hydroxymethyl, and a hydrogen atom or methyl is preferred.

[0168] In formula (III), * represents a bonding site with other structures.

[0169] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, cycloalkylene group, or polyalkyleneoxy group.

[0170] R 201 Preferred examples of R include alkylene groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butane diyl, 1,3-butane diyl, -CH2CH(OH)CH2-, polyalkyleneoxy group, more preferably alkylene groups such as vinyl and propenyl, -CH2CH(OH)CH2-, cyclohexyl, polyalkyleneoxy group, and further preferably alkylene groups such as vinyl and propenyl or polyalkyleneoxy group.

[0171] In the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different from each other.

[0172] 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, may be an arrangement having blocks, or may be an arrangement having a pattern such as an alternating pattern.

[0173] The number of carbon atoms of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon atoms of the substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, further preferably 2 to 5, still further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0174] Moreover, the above-mentioned alkylene group may have a substituent. Preferred examples of the substituent include an alkyl group, an aryl group, a halogen atom, and the like.

[0175] Moreover, the number of alkyleneoxy groups contained in the polyalkyleneoxy (the repeating number of the polyalkyleneoxy) is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.

[0176] As the polyalkyleneoxy, from the viewpoints of solvent solubility and solvent resistance, poly(ethyleneoxy), poly(propyleneoxy), poly(triethyleneoxy), poly(tetraethyleneoxy), or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, poly(ethyleneoxy) or poly(propyleneoxy) is more preferred, and poly(ethyleneoxy) 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 form a block for arrangement, or may be arranged in a pattern such as an alternating pattern. The preferred mode of the repeating number of ethyleneoxy groups and the like in these groups is as described above.

[0177] In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a conjugate salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0178] 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 silicon 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.

[0179] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0180] Moreover, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0181] Moreover, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as diamines, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be cited.

[0182] 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 a repeating unit represented by formula (2-A). By the polyimide precursor containing the repeating unit represented by formula (2-A), the range of exposure latitude can be further increased.

[0183] Formula (2-A)

[0184] [Chemical formula 17]

[0185]

[0186] 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.

[0187] 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 preferred ranges are also the same.

[0188] R 112 has the same meaning as R 112 in formula (5), and preferably the preferred ranges are also the same.

[0189] The polyimide precursor may contain one kind of repeating unit represented by the formula (2), or may contain two or more kinds. Moreover, it may contain a structural isomer of the repeating unit represented by the formula (2). And it is obvious that the polyimide precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (2).

[0190] As an embodiment of the polyimide precursor in the present invention, there can be cited a mode in which the content of the repeating unit represented by the formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals can be the repeating unit represented by the formula (2).

[0191] 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 further preferably 15,000 to 40,000. Moreover, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0192] The dispersity of the molecular weight of the above polyimide precursor 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 precursor 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.

[0193] In this specification, the dispersity of the molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight.

[0194] Moreover, when the resin composition contains a plurality of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the above plurality of polyimide precursors as one kind of resin are respectively within the above ranges.

[0195] [Polyimide]

[0196] The polyimide used in the present invention can be an alkali-soluble polyimide, or can also be a polyimide soluble in a developer mainly composed of an organic solvent.

[0197] In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formability, a polyimide that dissolves 0.5 g or more is preferred, and a polyimide that dissolves 1.0 g or more is more preferred. The upper limit of the above dissolution amount is not particularly limited, and 100 g or less is preferred.

[0198] Moreover, 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.

[0199] In this specification, the "main chain" refers to the relatively longest bonded chain in the molecule of the high molecular compound constituting the resin, and the "side chain" refers to the bonded chain other than that.

[0200] -fluorine atom-

[0201] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably further has a fluorine atom.

[0202] The fluorine atom is preferably included, for example, in 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 , and more preferably included as a fluorinated alkyl group in 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 .

[0203] The amount of the fluorine atom is preferably 5 mass% or more and, moreover, preferably 20 mass% or less with respect to the total mass of the polyimide.

[0204] -silicon atom-

[0205] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably further has a silicon atom.

[0206] The silicon atom is preferably included, for example, in R in the repeating unit represented by the following formula (4) 131 , and more preferably included as the following organically modified (poly)siloxane structure in R in the repeating unit represented by the following formula (4) 131 .

[0207] Moreover, the above silicon atom or the above 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.

[0208] The amount of the silicon atom is preferably 1 mass% or more and more preferably 20 mass% or less with respect to the total mass of the polyimide.

[0209] -ethylenically unsaturated bond-

[0210] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0211] The polyimide may have an ethylenically unsaturated bond at the main chain terminal or in the side chain, and preferably has it in the side chain.

[0212] The above-mentioned ethylenically unsaturated bond preferably has radical polymerizability.

[0213] The ethylenically unsaturated bond is preferably included in 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 and more preferably included as a group having an ethylenically unsaturated bond in 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 .

[0214] Among these, the ethylenically unsaturated bond is preferably included in R in the repeating unit represented by the following formula (4) 131 and more preferably included as a group having an ethylenically unsaturated bond in R in the repeating unit represented by the following formula (4) 131 .

[0215] Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which can be substituted and directly bonded to an aromatic ring, such as vinyl, allyl, vinylphenyl, (meth)acrylamide group, (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0216] [Chemical formula 18]

[0217]

[0218] 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.

[0219] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3) or a group formed by combining two or more of these.

[0220] Moreover, as the alkylene group having 2 to 12 carbon atoms, it can be any of a linear, branched, cyclic alkylene group or an alkylene group represented by a combination of these.

[0221] As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferred, and an alkylene group having 2 to 4 carbon atoms is more preferred.

[0222] Among these, R 21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

[0223] [Chemical formula 19]

[0224]

[0225] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these, X represents an oxygen atom or a sulfur atom, * represents a bonding site to other structures, and ● represents a bonding site to the oxygen atom bonded to R in formula (IV). 21 The bonding site of the oxygen atom bonded to

[0226] 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 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 the above R 21 above.

[0227] In formula (R1), X is preferably an oxygen atom.

[0228] In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred mode is also the same.

[0229] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a phenolic hydroxyl group or other hydroxyl groups with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.).

[0230] 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.).

[0231] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a phenolic hydroxyl group or other hydroxyl groups with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

[0232] In formula (IV), * represents a bonding site to other structures, preferably a bonding site to the main chain of the polyimide.

[0233] The amount of ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g, relative to the total mass of the polyimide.

[0234] - Polymerizable group other than the group having an ethylenically unsaturated bond -

[0235] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0236] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include epoxy group, cyclic ether groups such as oxetanyl group, alkoxymethyl groups such as methoxymethyl group, hydroxymethyl group, and the like.

[0237] For example, the polymerizable group other than the group having an ethylenically unsaturated bond preferably includes R in the repeating unit represented by formula (4) described later. 131 。

[0238] The amount of the polymerizable group other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, relative to the total mass of the polyimide.

[0239] - Polarity conversion group -

[0240] 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.

[0241] The polarity conversion group is included, for example, in R in the repeating unit represented by formula (4) described later 131 , R 132 , the terminal of the polyimide, and the like.

[0242] - Acid value -

[0243] 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 further preferably 70 mgKOH / g or more.

[0244] Moreover, the above acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and further preferably 200 mgKOH / g or less.

[0245] Moreover, when using polyimide in development with a developer mainly composed of an organic solvent (for example, "solvent development" described later), 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.

[0246] The above acid value is measured by a known method. For example, it is measured by the method described in JIS K 0070:1992.

[0247] Moreover, as the acid group contained in the polyimide, from the viewpoint of balancing storage stability and developability, an acid group with a pKa of 0 to 10 is preferred, and an acid group with a pKa of 3 to 8 is more preferred.

[0248] pKa is expressed as the negative common logarithm pKa of the equilibrium constant Ka in consideration of the dissociation reaction in which an acid releases hydrogen ions. In this specification, unless otherwise specified, the pKa is set as the calculated value based on ACD / ChemSketch (registered trademark). Alternatively, the values described in "Revised 5th Edition Chemistry Handbook Basic Volume" edited by the Chemical Society of Japan can be referred to.

[0249] Moreover, when the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0250] The polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group as such an acid group, and more preferably contains a phenolic hydroxyl group.

[0251] -Phenolic hydroxyl group-

[0252] From the viewpoint of making the development rate based on an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0253] The polyimide may have a phenolic hydroxyl group at the main chain end or on the side chain.

[0254] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the following formula (4) described later 132 or R in the repeating unit represented by the following formula (4) described later 131 .

[0255] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, relative to the total mass of the polyimide.

[0256] As the polyimide used in the present invention, as long as it is a high molecular compound having an imide structure, it is not particularly limited, and preferably contains a repeating unit represented by the following formula (4).

[0257] [Chemical formula 20]

[0258]

[0259] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.

[0260] When there is a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132 , and as shown in the following formula (4-1) or formula (4-2), it may be located at the end of the polyimide.

[0261] Formula (4-1)

[0262] [Chemical formula 21]

[0263]

[0264] In formula (4-1), R 133 is a polymerizable group, and the meanings of other groups are the same as those in formula (4).

[0265] Formula (4-2)

[0266] [Chemical formula 22]

[0267]

[0268] R 134 and R 135 At least one of them is a polymerizable group, and in the case where it is not a polymerizable group, it is an organic group, and the meanings of other groups are the same as those in formula (4).

[0269] As the polymerizable group, a group containing the above vinyl unsaturated bond or a crosslinkable group other than the group containing the above vinyl unsaturated bond can be cited.

[0270] R 131 represents a divalent organic group. As the divalent organic group, groups the same as R 111 in formula (2) can be exemplified, and the preferred ranges are also the same.

[0271] Moreover, as R 131 , a diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamines, etc. can be cited. As a specific example, an example of R 111 in formula (2) of the polyimide precursor can be cited.

[0272] From the viewpoint of more effectively suppressing warping during formation, R 131Preferably a diamine residue having at least 2 alkylene glycol units in the main chain. More preferably a diamine containing in one molecule a total of 2 or more ethylene glycol chains, propylene glycol chains, any one or both of them, and still more preferably a diamine residue which is the above diamine and does not contain an aromatic ring.

[0273] Examples of the diamine containing in one molecule a total of 2 or more ethylene glycol chains, propylene glycol chains, any one or both of them include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (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., but are not limited to these.

[0274] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include the same group as R in formula (2), and the preferred range is also the same. 115 Same as above.

[0275] For example, as R 115 The four bonding bonds of the tetravalent organic group exemplified form a condensed ring by bonding to the four -C(=O)- parts in the above formula (4).

[0276] Moreover, R 132 Examples include a tetracarboxylic acid residue remaining after removing the acid anhydride group from a tetracarboxylic dianhydride. As a specific example, examples of R in formula (2) of a polyimide precursor can be given. From the viewpoint of the strength of the organic film, R 115 is preferably an aromatic diamine residue having 1 to 4 aromatic rings. 132 Same as above.

[0277] It is also preferred 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, the above (DA-1) to (DA-18) as preferred examples, and as R 132 , examples include the above (DAA-1) to (DAA-5) as more preferred examples.

[0278] Furthermore, the polyimide preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0279] Moreover, 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.

[0280] Moreover, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are capped with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloroacyl compound, an active monoester compound, etc. Among these, it is more preferable to use a monoamine. As the preferred compounds 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 various different end groups can also be introduced by reacting a plurality of capping agents.

[0281] -Imidization rate (ring closure rate)-

[0282] 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.

[0283] The upper limit of the above imidization rate is not particularly limited, and it may be 100% or less.

[0284] For example, the above imidization rate can be measured by the following method.

[0285] Measure the infrared absorption spectrum of the polyimide, and obtain the absorption peak derived from the imide structure, that is, the peak intensity P1 around 1377 cm -1 Then, after heat-treating the polyimide at 350 °C for 1 hour, measure the infrared absorption spectrum again, and obtain 1377 cm-1 The peak intensity P2 in the vicinity. Using the obtained peak intensities P1 and P2, the imidization ratio of the polyimide can be obtained according to the following formula.

[0286] Imidization ratio (%) = (peak intensity P1 / peak intensity P2) × 100

[0287] The polyimide may have a repeating unit represented by the above formula (4) containing all of one kind of R 131 or R 132 and may also have a repeating unit represented by the above formula (4) containing two or more different kinds of R 131 or R 132 Moreover, in addition to the repeating unit represented by the above formula (4), the polyimide may also contain other kinds of repeating units. As other kinds of repeating units, for example, a repeating unit represented by the above formula (2) etc. can be cited.

[0288] For example, the polyimide can be synthesized as follows: by using a method of reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine i.e., a capping agent) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially substituted with an acid anhydride or a monoacyl chloride compound or an active monoester compound i.e., a capping agent) with a diamine at a low temperature, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine (partially substituted with a monoamine i.e., a capping agent) and a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then acyl chlorinating the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine i.e., a capping agent), etc. to obtain a polyimide precursor, and using a method of completely imidizing it by a conventional imidization reaction method or a method of stopping the imidization reaction halfway and introducing a part of the imide structure, a method of introducing a part of the imide structure by further mixing a completely imidized polymer and its polyimide precursor to synthesize. Moreover, other known polyimide synthesis methods can also be applied.

[0289] 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 bend resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (for example, elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more.

[0290] Moreover, 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.

[0291] The dispersity of the molecular weight of the polyimide described above 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.

[0292] Moreover, when the resin composition contains a plurality of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above ranges. Further, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the above plurality of polyimides as one resin are respectively within the above ranges.

[0293] 〔Polyphenylene Oxazole Precursor〕

[0294] Regarding the polyphenylene oxazole precursor used in the present invention, its structure is not particularly limited, and it preferably contains a repeating unit represented by the following formula (3).

[0295] [Chemical Formula 23]

[0296]

[0297] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.

[0298] In formula (3), R 123 and R 124 have the same meanings as R 113 in formula (2), and the preferred ranges are also the same. That is, it is preferable that at least one is a polymerizable group.

[0299] In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a linear aliphatic group is preferred. R 121 is preferably a dicarboxylic acid residue. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0300] As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.

[0301] As the dicarboxylic acid containing an aliphatic group, it is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 - 30, more preferably 2 - 25, further preferably 3 - 20, still more preferably 4 - 15, and particularly preferably 5 - 10. The linear aliphatic group is preferably an alkylene group.

[0302] As the dicarboxylic acid containing a linear aliphatic group, examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecafluorosebacate, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, henicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formula, etc.

[0303] [Chemical formula 24]

[0304]

[0305] (In the formula, Z is a hydrocarbon group having 1 - 6 carbon atoms, and n is an integer of 1 - 6.)

[0306] As the dicarboxylic acid containing an aromatic group, it is preferably a dicarboxylic acid having the following aromatic group, and more preferably a dicarboxylic acid composed only of a group having the following aromatic group and two -COOH groups.

[0307] [Chemical formula 25]

[0308]

[0309] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * each independently represents a bonding site to other structures.

[0310] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0311] In formula (3), R 122 represents a tetravalent organic group. As the tetravalent organic group, it has the same meaning as R in the above formula (2) 115 and the preferred range is also the same.

[0312] Moreover, R 122 is preferably a group derived from a diaminophenol derivative. As the group derived from a diaminophenol derivative, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. can be cited. These diaminophenols can be used alone or in combination.

[0313] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic group are preferred.

[0314] [Chemical formula 26]

[0315]

[0316] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, * and # respectively represent the bonding sites with other structures. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Moreover, R 122 is also preferably a structure represented by the above formula. When R 122 is a structure represented by the above formula, among the total 4 * and #, preferably any 2 are the bonding sites of the nitrogen atom bonded to R in formula (3) 122 and the other 2 are the bonding sites of the nitrogen atom bonded to R in formula (3) 122The bonding site of the bonded oxygen atom, more preferably 2 *'s are to R in formula (3) 122 The bonding site of the bonded oxygen atom and 2 #'s are to R in formula (3) 122 The bonding site of the bonded nitrogen atom or 2 *'s are to R in formula (3) 122 The bonding site of the bonded nitrogen atom and 2 #'s are to R in formula (3) 122 The bonding site of the bonded oxygen atom, further preferably 2 *'s are to R in formula (3) 122 The bonding site of the bonded oxygen atom and 2 #'s are to R in formula (3) 122 The bonding site of the bonded nitrogen atom.

[0317] The diaminophenol derivative is also preferably a compound represented by formula (A-s).

[0318] [Chemical formula 27]

[0319]

[0320] In formula (A-s), R1 is an organic group selected from a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond or the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, a cyclic alkyl group, and they may be the same or different. R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, a cyclic alkyl group, and they may be the same or different.

[0321] [Chemical formula 28]

[0322]

[0323] (In formula (A-sc), * represents bonding to the aromatic ring of the aminophenol group of the diaminophenol derivative represented by the above formula (A-s).)

[0324] It is considered that in the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, makes the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and is particularly preferred in terms of further improving the effect that the cyclization rate is higher during curing at low temperature.

[0325] Moreover, in the above formula (A-s), when R2 is an alkyl group and R3 is an alkyl group, the high transparency to i-rays and the effect of a high cyclization rate during curing at low temperature can be maintained, so it is preferred.

[0326] Moreover, in the above formula (A-s), R1 is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group involved in R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, from the aspects of maintaining high transparency to i-rays, having a high cyclization rate during curing at low temperature, having sufficient solubility in a solvent, and obtaining a polybenzoxazole precursor with excellent overall properties, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred.

[0327] As a method for manufacturing the diaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506 can be referred to, and these contents are incorporated herein.

[0328] Specific examples of the structure of the diaminophenol derivative represented by the above formula (A-s) include the contents described in paragraphs 0070 to 0080 of Japanese Patent Application Laid-Open No. 2013-256506, and these contents are incorporated herein. Of course, it is not limited to these.

[0329] In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may further contain other types of repeating units.

[0330] From the aspect of being able to suppress warping accompanying the ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as other types of repeating units.

[0331] [Chemical formula 29]

[0332]

[0333] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms, and R 3s , R 4s , R 5s , R 6s at least one of them is an aromatic group, and the remaining part is a hydrogen atom or an organic group having 1 to 30 carbon atoms and can be the same or different respectively. The polymerization of the a structure and the b structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

[0334] In formula (SL), as a preferred Z, R 5s and R 6sis phenyl. Moreover, the molecular weight of the structure represented by the formula (SL) is preferably from 400 to 4,000, more preferably from 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be more effectively reduced, and the effects of suppressing warping and improving solvent solubility can be taken into account.

[0335] When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, it is also preferably further contains a tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R in the formula (2). 115 as an example.

[0336] For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 18,000 to 30,000, more preferably from 20,000 to 29,000, and further preferably from 22,000 to 28,000. Moreover, the number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and further preferably from 9,200 to 11,200.

[0337] The dispersity of the molecular weight of the above polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit value of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly limited. For example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, still further preferably 2.3 or less, and even further preferably 2.2 or less.

[0338] Moreover, when the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the above plurality of polybenzoxazole precursors as one resin are within the above ranges respectively.

[0339] [Polybenzoxazole]

[0340] As the polybenzoxazole, as long as it is a high molecular compound having a benzoxazole ring, it is not particularly limited. A compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the above polymerizable group, a radical polymerizable group is preferred. Moreover, it can be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.

[0341] [Chemical formula 30]

[0342]

[0343] In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group.

[0344] When there is a polarity-converting group such as a polymerizable group or an acid-decomposable group, the polarity-converting group such as a polymerizable group or an acid-decomposable group may be located on at least one of R 133 and R 134 and may also be located at the end of polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0345] Formula (X-1)

[0346] [Chemical formula 31]

[0347]

[0348] In formula (X-1), at least one of R 135 and R 136 is a polarity-converting group such as a polymerizable group or an acid-decomposable group, and is an organic group when it is not a polarity-converting group such as a polymerizable group or an acid-decomposable group. The meanings of other groups are the same as those in formula (X).

[0349] Formula (X-2)

[0350] [Chemical formula 32]

[0351]

[0352] In formula (C-2), R 137 is a polarity-converting group such as a polymerizable group or an acid-decomposable group, and the rest are substituents. The meanings of other groups are the same as those in formula (X).

[0353] The polarity-converting group such as a polymerizable group or an acid-decomposable group has the same meaning as the polymerizable group described in the polymerizable groups possessed by the above polyimide precursor.

[0354] R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group or an aromatic group. As a specific example, examples of R 121 in formula (3) of the polybenzoxazole precursor can be cited. Moreover, its preferred examples have the same meaning as R 121

[0355] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include examples of R 122 in formula (3) of the polybenzoxazole precursor. Moreover, its preferred examples have the same meaning as R 122

[0356] For example, as R122 The four bonding bonds of the exemplified tetravalent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is the following organic group, the following structure is formed. In the following structure, * respectively represents the bonding sites with the nitrogen atom or the oxygen atom in the formula (X).

[0357] [Chemical formula 33]

[0358]

[0359] The oxazolization rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited and can be 100%. When the oxazolization rate is 85% or more, the film shrinkage based on the ring closure (which occurs when it is oxazolized by heating) becomes smaller, and warpage can be effectively suppressed.

[0360] For example, the above oxazolization rate can be measured by the following method.

[0361] Measure the infrared absorption spectrum of polybenzoxazole, and find the absorption peak of the amide structure derived from the precursor, that is, the peak intensity Q1 around 1650 cm -1 Next, normalization is performed using the absorption intensity of the aromatic ring observed around 1490 cm -1 After heat-treating the polybenzoxazole precursor at 350 °C for 1 hour, measure the infrared absorption spectrum again, find the peak intensity Q2 around 1650 cm -1 Next, normalization is performed using the absorption intensity of the aromatic ring observed around 1490 cm -1 Using the normalized values of the obtained peak intensities Q1 and Q2, the oxazolization rate of polybenzoxazole can be obtained according to the following formula.

[0362] Oxazolization rate (%) = (normalized value of peak intensity Q1 / normalized value of peak intensity Q2) × 100

[0363] Polybenzoxazole can have repeating units of the above formula (X) all of which are one kind of R 131 or R 132 It can also have repeating units of the above formula (X) containing two or more different kinds of R 131 or R 132 Moreover, in addition to the repeating units of the above formula (X), polybenzoxazole can also contain other kinds of repeating units.

[0364] For example, polybenzoxazole can be obtained as follows: reacting a diamino-phenol derivative with a compound containing R 133React with a dicarboxylic acid or a compound such as a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the above-mentioned dicarboxylic acids to obtain a polybenzoxazole precursor, and make it undergo oxazolization using the conventional oxazolization reaction method.

[0365] In addition, in the case of a dicarboxylic acid, in order to improve the reaction yield, etc., an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole, etc. can also be used.

[0366] The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bend resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[0367] Moreover, the number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200.

[0368] The dispersity of the molecular weight of the above-mentioned polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit value of the dispersity of the molecular weight of the polybenzoxazole is not particularly limited. For example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, still further preferably 2.3 or less, and even further preferably 2.2 or less.

[0369] Moreover, when the resin composition contains a plurality of polybenzoxazoles as specific resins, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least one polybenzoxazole are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the dispersity calculated for the above-mentioned plurality of polybenzoxazoles as one resin are respectively within the above ranges.

[0370] [Polyamideimide precursor]

[0371] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

[0372] [Chemical formula 34]

[0373]

[0374] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.

[0375] In formula (PA1-2), R 117 may be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these via a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these via a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0376] As the above linking group, -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferred.

[0377] As the above alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0378] As the above halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. Moreover, as the halogen atom in the above halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be mentioned, and a fluorine atom is preferred. The above halogenated alkylene group may have a hydrogen atom and all hydrogen atoms may be substituted by halogen atoms, and it is preferred that all hydrogen atoms are substituted by halogen atoms. As an example of a preferred halogenated alkylene group, (difluoromethyl)methylene, etc. may be mentioned.

[0379] As the above arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is further preferred.

[0380] Moreover, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. As the above halogenation, chlorination is preferred.

[0381] In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound.

[0382] Two of the three carboxyl groups of the above tricarboxylic acid compound can be anhydrified.

[0383] Examples of the tricarboxylic acid compound that can be halogenated and used for producing a polyamideimide precursor include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds and the like.

[0384] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0385] Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound including a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these via a single bond or a linking group is preferred, and a tricarboxylic acid compound including an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0386] Moreover, specific examples of the tricarboxylic acid compound include 1,2,3 - propane tricarboxylic acid, 1,3,5 - pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3,6 - naphthalene tricarboxylic acid, a compound formed by linking phthalic acid (or phthalic anhydride) and benzoic acid via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group, and the like.

[0387] These compounds may be a compound formed by anhydrating two carboxyl groups (for example, trimellitic anhydride), or may be a compound formed by halogenating at least one carboxyl group (for example, trichloromethyl trimellitate).

[0388] In formula (PAI - 2), R 111 , A 2 , R 113 have the same meanings as R 111 , A 2 , R 113 in formula (2) above, and the preferred modes are also the same.

[0389] The polyamideimide precursor may further contain other repeating units.

[0390] Examples of the other repeating units include the repeating unit represented by formula (2) above, the repeating unit represented by formula (PAI - 1) below, and the like.

[0391] [Chemical formula 35]

[0392]

[0393] In formula (PAI - 1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group.

[0394] In formula (PAI-1), R 116 may be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0395] As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a haloalkylene group, an arylene group, or a linking group formed by bonding two or more of these is preferred. More preferably, -O-, -S-, an alkylene group, a haloalkylene group, an arylene group, or a linking group formed by bonding two or more of these is preferred.

[0396] As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0397] As the above-mentioned haloalkylene group, a haloalkylene group having 1 to 20 carbon atoms is preferred, a haloalkylene group having 1 to 10 carbon atoms is more preferred, and a haloalkylene group having 1 to 4 carbon atoms is further preferred. Moreover, as the halogen atom in the above-mentioned haloalkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be cited, and a fluorine atom is preferred. The above-mentioned haloalkylene group may have a hydrogen atom and all hydrogen atoms may be substituted by a halogen atom. Preferably, all hydrogen atoms are substituted by a halogen atom. As an example of a preferred haloalkylene group, (difluoromethyl)methylene, etc. can be cited.

[0398] As the above-mentioned arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is further preferred.

[0399] Moreover, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

[0400] In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halocarboxyl groups is called a dicarboxylic acid dihalide compound.

[0401] The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, and is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0402] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound that can be halogenated and used for manufacturing a polyamideimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds, etc.

[0403] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds can be used alone or in combination of two or more.

[0404] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a dicarboxylic acid compound or dicarboxylic acid dihalide compound preferably containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cycloaliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more of these via a single bond or a linking group is more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0405] Moreover, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, henicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0406] Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups in the specific examples of the above dicarboxylic acid compounds are halogenated.

[0407] In formula (PAI-1), R 111 is the same as R in the above formula (2) 111They have the same meaning and the same preferred mode.

[0408] Moreover, the polyamideimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0409] Moreover, for the purpose of improving the adhesion to the substrate, the polyamideimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, examples include the use of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0410] As one embodiment of the polyamideimide precursor in the present invention, an example is a mode in which the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals can be any one of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2).

[0411] Moreover, as another embodiment of the polyamideimide precursor in the present invention, an example is a mode in which the total content of the repeating unit represented by formula (PAI-2) and the repeating unit represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals can be any one of the repeating unit represented by formula (PAI-2) or the repeating unit represented by formula (PAI-1).

[0412] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0413] The dispersity of the molecular weight of the polyamideimide 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 polyamideimide 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. Moreover, when the resin composition contains a plurality of polyamideimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide precursor are within the above ranges. Further, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the plurality of polyamideimide precursors as one resin are within the above ranges respectively.

[0414] [Polyamideimide]

[0415] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer mainly composed of an organic solvent.

[0416] In this specification, an alkali-soluble polyamideimide means a polyamideimide that dissolves 0.1 g or more in 100 g of a 2.38 mass% aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formability, it is preferably a polyamideimide that dissolves 0.5 g or more, and still more preferably a polyamideimide that dissolves 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited and is preferably 100 g or less.

[0417] Moreover, from the viewpoints of the film strength and insulation of the obtained organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0418] -Fluorine atom-

[0419] From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has a fluorine atom.

[0420] The fluorine atom is preferably contained in, for example, R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 , and more preferably contained as a fluorinated alkyl group in R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 .

[0421] The amount of the fluorine atom is preferably 5 mass% or more and preferably 20 mass% or less relative to the total mass of the polyamideimide.

[0422] -Ethylenically unsaturated bond-

[0423] From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

[0424] The polyamideimide may have ethylenically unsaturated bonds at the main chain terminals or at the side chains, preferably at the side chains.

[0425] The above-mentioned ethylenically unsaturated bonds preferably have radical polymerizability.

[0426] The ethylenically unsaturated bonds are preferably included in R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 , and more preferably included as a group having an ethylenically unsaturated bond in R in the repeating unit represented by the following formula (PAI-3) 117 or R 111 .

[0427] The preferred mode of the group having an ethylenically unsaturated bond is the same as that of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0428] Relative to the total mass of the polyamideimide, the amount of the ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0429] -Polymerizable group other than ethylenically unsaturated bond-

[0430] The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond.

[0431] As the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide, the same groups as those of the polymerizable group other than the ethylenically unsaturated bond in the above-mentioned polyimide can be cited.

[0432] For example, the polymerizable group other than the ethylenically unsaturated bond is preferably included in R in the repeating unit represented by the following formula (PAI-3) 111 .

[0433] Relative to the total mass of the polyamideimide, the amount of the polymerizable group other than the ethylenically unsaturated bond is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0434] -Polarity conversion group-

[0435] The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is the same as the acid-decomposable group described in R in the above formula (2) 113 and R 114 , and the preferred mode is also the same.

[0436] -Acid value-

[0437] When polyamideimide is used for alkali development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.

[0438] Moreover, 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.

[0439] Moreover, when polyamideimide is used in development with a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and still more preferably 5 to 20 mgKOH / g.

[0440] The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0441] Moreover, as the acid group contained in the polyamideimide, the same groups as the acid groups in the above polyimide can be cited, and the preferred modes are also the same.

[0442] -Phenolic hydroxyl group-

[0443] From the viewpoint of making the development rate based on the alkali developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

[0444] The polyamideimide may have a phenolic hydroxyl group at the main chain end or on the side chain.

[0445] The phenolic hydroxyl group is preferably included in R in the repeating unit represented by the following formula (PAI-3), for example. 117 or R 111 .

[0446] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, based on the total mass of the polyamideimide.

[0447] As the polyamideimide used in the present invention, as long as it is a high molecular compound having an imide structure and an amide bond, there is no particular limitation, and it preferably contains a repeating unit represented by the following formula (PAI-3).

[0448] [Chemical formula 36]

[0449]

[0450] In formula (PAI-3), R 111 and R 117 are respectively the same as R in formula (PAI-2).111 and R 117 have the same meaning and the same preferred mode.

[0451] When having a polymerizable group, the polymerizable group may be located on at least one of R 111 and R 117 and may also be located at the end of the polyamideimide.

[0452] Moreover, in order to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of the polyamideimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, an active monoester compound, etc. The preferred mode of the capping agent is the same as that of the capping agent in the above polyimide.

[0453] -Imidization rate (ring closure rate)-

[0454] 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 polyamideimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

[0455] The upper limit of the above imidization rate is not particularly limited and may be 100% or less.

[0456] The above imidization rate can be measured by the same method as the ring closure rate of the above polyimide.

[0457] The polyamideimide may have a repeating unit represented by the above formula (PAI-3) containing all of one kind of R 111 or R 117 and may also have a repeating unit represented by the above formula (PAI-3) containing two or more different kinds of R 131 or R 132 Moreover, in addition to the repeating unit represented by the above formula (PAI-3), the polyamideimide may contain other kinds of repeating units. As other kinds of repeating units, repeating units represented by the above formula (PAI-1) or formula (PAI-2) etc. can be cited.

[0458] The polyamideimide can be synthesized, for example, as follows: obtaining a polyamideimide precursor by a known method and using a method of completely imidizing it by a conventional imidization reaction method or a method of stopping the imidization reaction halfway and introducing a part of the imide structure, or a method of introducing a part of the imide structure by further mixing a completely imidized polymer and the polyamideimide precursor.

[0459] The weight-average molecular weight (Mw) of the polyamideimide is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and still more preferably from 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or more, the bend resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more.

[0460] Moreover, the number-average molecular weight (Mn) of the polyamideimide is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and still more preferably from 4,000 to 25,000.

[0461] The dispersity of the molecular weight of the polyamideimide 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 polyamideimide 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.

[0462] Moreover, when the resin composition contains a plurality of polyamideimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide are within the above ranges. Moreover, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated for the plurality of polyamideimides as one resin are within the above ranges, respectively.

[0463] 〔Method for producing polyimide precursor, etc.〕

[0464] For example, a polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at a 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 halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine, etc. Among the above production methods, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferable.

[0465] Examples of the above condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc.

[0466] 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.

[0467] Examples of the above halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, etc.

[0468] In the production method of a polyimide precursor or the like, an organic solvent is preferably used during the reaction. The organic solvent may be one kind or two or more kinds.

[0469] The organic solvent can be appropriately determined according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0470] In the production method of a polyimide precursor or the like, a basic compound is preferably added during the reaction. The basic compound may be one kind or two or more kinds.

[0471] 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, etc.

[0472] -End-capping agent-

[0473] When manufacturing polyimide precursors and the like, in order to further improve storage stability, it is preferable to cap the carboxylic anhydride, acid anhydride derivative or amino group remaining at the resin terminal of the polyimide precursor and the like. When capping the carboxylic anhydride and acid anhydride derivative remaining at the resin terminal, as the capping agent, monohydric alcohols, phenols, thiols, benzenethiols, monoamines, etc. can be cited. Considering reactivity and film stability, it is more preferable to use monohydric alcohols, phenols, and monoamines. As preferred compounds of monohydric alcohols, primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc., secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc., and tertiary alcohols such as butanol, adamantanol, etc. can be cited. As preferred compounds of phenols, phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, hydroxystyrene, etc. can be cited. Moreover, as preferred compounds of monoamines, 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 various different terminal groups can also be introduced by reacting multiple capping agents.

[0474] Moreover, when capping the amino group at the lipid terminal, a compound having a functional group capable of reacting with the amino group can be used for capping. Preferred capping 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. As preferred compounds of carboxylic anhydrides, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be cited. Moreover, as preferred compounds of carboxylic acid chlorides, 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. can be cited.

[0475] -Solid precipitation-

[0476] The manufacturing method of a polyimide precursor, etc. may include a step of precipitating a solid. Specifically, after filtering out, if necessary, the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution, the obtained polymer component is put into a poor solvent such as water, a lower aliphatic alcohol 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 of the polyimide precursor, etc. can be repeated. A step of removing ionic impurities using an ion exchange resin may further be included.

[0477] 〔Content〕

[0478] 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, still more preferably 50% by mass or more, relative to the total solid content of the resin composition. Moreover, 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, still more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solid content of the resin composition.

[0479] The resin composition of the present invention may contain only one kind of specific resin, or may contain two or more kinds. When containing two or more kinds, the total amount is preferably within the above range.

[0480] Moreover, the resin composition of the present invention preferably further contains at least two kinds of resins.

[0481] 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.

[0482] When the resin composition of the present invention contains two or more kinds of specific resins, it preferably contains, for example, two or more kinds of polyimide precursors having different structures derived from dianhydrides (R in the above formula (2)) 115 ).

[0483] <Other resins>

[0484] The resin composition of the present invention may contain other resins (hereinafter, also simply referred to as "other resins") different from the specific resin in addition to or instead of the above specific resin.

[0485] Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, polyester resins, and the like.

[0486] In particular, by using a (meth)acrylic resin having an acid-decomposable group, the resin composition can be used as a composition for forming a pattern. Examples of the (meth)acrylic resin having such an acid-decomposable group include resin (B) described in paragraphs 0069 to 0170 of Japanese Patent Application Laid-Open No. 2019-174549.

[0487] Moreover, 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.

[0488] For example, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1×10 -3 mol / g or more) to the resin composition in place of or in addition to the polymerizable compound described below, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.

[0489] 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, relative to the total solid content of the resin composition.

[0490] Moreover, 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, relative to the total solid content of the resin composition.

[0491] Moreover, as a preferred embodiment of the resin composition of the present invention, a form with a low content of other resins can also be adopted. In the above form, the content of the other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, still further preferably 5% by mass or less, and even further preferably 1% by mass or less, relative to the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0492] The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0493] <Specific base generator>

[0494] The resin composition of the present invention contains a base generator (specific base generator) represented by formula (1-1).

[0495] [Chemical formula 37]

[0496]

[0497] In formula (1-1), each R is independently a hydrogen atom or a monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs may be linked to form a ring structure. OH described in formula (1-1) represents a hydroxyl group, L is a divalent organic group, and has at least one heteroatom on the linking chain of the shortest path connecting the adjacent oxygen atom and carbon atom.

[0498] [R]

[0499] From the viewpoint of the elongation at break of the cured product, in formula (1-1), each R preferably independently represents a monovalent organic group.

[0500] R is preferably a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group, or a group represented by a combination thereof, still more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by a combination thereof, and particularly preferably an alkyl group having 1 to 10 carbon atoms.

[0501] As the above alkyl group, it may be any of linear, branched, and cyclic. From the viewpoint of improving the elongation at break, a branched alkyl group (for example, isopropyl, isobutyl, 2-ethylhexyl, etc.) or a cyclic alkyl group (for example, cyclohexyl, etc.) is preferred.

[0502] R may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, a hydroxyl group, a group represented by the following formula (R-1), etc.

[0503] [Chemical formula 38]

[0504]

[0505] In formula (R-1), R a represents a monovalent organic group, R b represents a divalent organic group, n represents an integer of 1 or more, m represents 0 or 1, and * represents a bonding site with other structures.

[0506] In formula (R-1), R aPreferably a hydrocarbon group, more preferably an alkyl group, and still more preferably an alkyl group having 1 to 10 carbon atoms.

[0507] In formula (R-1), R b Preferably a hydrocarbon group, more preferably an alkylene group, still more preferably an alkylene group having 2 to 10 carbon atoms, particularly preferably an alkylene group having 2 to 4 carbon atoms, and most preferably a vinyl group or a propenyl group. When n is 2 or more, there are n Rs in formula (R-1) b They may be the same or different from each other.

[0508] In formula (R-1), it is preferably an integer of 1 to 10.

[0509] In formula (R-1), m is preferably 1.

[0510] As the ring structure formed by bonding two Rs in formula (1-1), for example, a piperidine ring, a morpholine ring, etc. having the nitrogen atom contained in the above amide bond as a ring member can be cited. These ring structures may further have substituents. As the substituents, the same groups as the substituents in the above hydrocarbon group can be cited.

[0511] Moreover, in formula (1-1), it is also preferred that at least one of the Rs is a structure represented by formula (R-2).

[0512] Since at least one of the Rs is a structure represented by formula (R-2), the volume around the nitrogen atom of the amino group in the resulting base becomes large, and thus the reaction with the resin in the film can be inhibited by steric hindrance. As a result, the base easily diffuses more uniformly in the film. Therefore, it is considered that it is easy to suppress the difference in the film shrinkage degree between the surface side and the substrate side of the film, and thus the rectangularity of the obtained pattern is further excellent.

[0513] [Chemical formula 39]

[0514]

[0515] In formula (R-2), R 2 and R 4 each independently represents a monovalent organic group, and the two Rs 2 with each other or R 2 and the other R in R in formula (1-1) (that is, when one of the two Rs in formula (1-1) is represented by formula (R-2), the other R in formula (1-1). The other R may also be a structure represented by formula (R-2)) may be linked to form a ring structure.

[0516] In formula (R-2), R 2Preferably a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group or a group represented by a combination thereof, still more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or a group represented by a combination thereof, and particularly preferably an alkyl group having 1 to 10 carbon atoms.

[0517] As the above alkyl group, it may be any of linear, branched and cyclic. From the viewpoint of improving the elongation at break, a branched alkyl group (e.g., isopropyl, isobutyl, 2-ethylhexyl, etc.) or a cyclic alkyl group (e.g., cyclohexyl, etc.) is preferred.

[0518] As two Rs 2 with each other or R 2 The ring structure formed by linking with another R in R in formula (1-1), for example, a piperidine ring, a morpholine ring, etc. having the nitrogen atom contained in the above amide bond as a ring member can be cited. These ring structures may further have substituents. As the substituents, the same groups as the substituents in the above hydrocarbon group can be cited.

[0519] As an example of the preferred form of R, the following structures can be cited, but are not limited thereto. The nitrogen atom contained in the structure of the following specific examples refers to the nitrogen atom contained in the amide bond in formula (1-1). In the following specific examples, * represents the bonding site with the carbonyl group.

[0520] [Chemical formula 40]

[0521]

[0522] Moreover, the dimethylpiperidine ring in the above structure has a cis form and a trans form, and either can be used. Here, from the viewpoint of the elongation at break of the obtained cured product, the cis form is preferred.

[0523] Compared with the cis form, the volume around the nitrogen atom becomes slightly larger in the trans form. Thus, in the cis form, the matrix compound is more likely to approach the nitrogen atom at the active site, and the effect of promoting imidization is improved. On the other hand, since it has a sufficiently large volume not to react with the resin, the pattern rectangularity can also be maintained. Therefore, compared with the trans form, the cis form has excellent elongation at break while maintaining other properties.

[0524] [L]

[0525] In formula (1-1), L is a divalent organic group and has at least one heteroatom on the linking chain of the shortest path connecting the adjacent oxygen atom (i.e., the oxygen atom in the OH group in formula (1-1)) and the carbon atom (i.e., the carbon atom in the carbonyl group in formula (1-1)).

[0526] Having at least one heteroatom on the connecting chain of the shortest path means that a heteroatom is included in the connecting chain with the minimum number of atoms in the chain connecting the oxygen atom in the OH group in formula (1-1) and the carbon atom in the carbonyl group in formula (1-1).

[0527] L may have only one heteroatom or may have two or more. Moreover, L may have only one heteroatom or may have two or more on the connecting chain of the shortest path described above.

[0528] As the heteroatom present on the connecting chain of the shortest path included in L of formula (1-1), examples include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, etc., and a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[0529] In particular, from the viewpoint of drug resistance, a nitrogen atom is preferred, and from the viewpoint of elongation at break, an oxygen atom or a sulfur atom is preferred.

[0530] In formula (1-1), L is preferably a group represented by a bond of one or more hydrocarbon groups and at least one structure selected from -O-, -S-, -NR N -, -P(=O)(OR P )O- and -SiR P 2-, and more preferably a group represented by a bond of one or more hydrocarbon groups and at least one structure selected from -0-, -S- and -NR N -. R N 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.

[0531] As the above hydrocarbon group, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by a bond of these is preferred.

[0532] As the above saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred. Moreover, in the present invention, unless otherwise particularly limited, the descriptions of saturated aliphatic hydrocarbon groups, alkyl groups, alkenyl groups, alkylene groups, etc. include any of linear, branched, cyclic or structures represented by combinations of these.

[0533] As the above unsaturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms is preferred, and an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is more preferred.

[0534] As the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms can be cited, and a group formed by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring is preferred, and a group formed by removing a plurality of hydrogen atoms from a benzene ring is more preferred.

[0535] From the viewpoints of the elongation at break and chemical resistance of the obtained cured product, the linking group preferably contains an aliphatic hydrocarbon ring group or an aromatic hydrocarbon group as the above-mentioned hydrocarbon group, more preferably contains an aromatic hydrocarbon group, and further preferably contains a group formed by removing a plurality of hydrogen atoms from a benzene ring.

[0536] The above-mentioned aliphatic hydrocarbon ring group is not particularly limited, and examples thereof include a group formed by removing a plurality of hydrogen atoms from a dicyclopentane ring, a cyclopentene ring, a norbornene ring, an isonorbornene ring, or an adamantane ring.

[0537] As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms can be mentioned, preferably a group formed by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably a group formed by removing a plurality of hydrogen atoms from a benzene ring.

[0538] Moreover, the above-mentioned aromatic hydrocarbon group or the above-mentioned aliphatic hydrocarbon ring group may be condensed with other rings. Examples of such a mode include a group formed by removing a plurality of hydrogen atoms from an indole ring, a benzofuran ring, a benzothiophene ring, or a dihydrodicyclopentene ring.

[0539] From the viewpoints of the elongation at break and chemical resistance of the obtained cured product, L preferably contains an aromatic hydrocarbon group as the above-mentioned hydrocarbon group, and more preferably contains a group formed by removing a plurality of hydrogen atoms from a benzene ring.

[0540] Moreover, from the viewpoint of base generation efficiency, when L contains an aromatic hydrocarbon group, it is further preferred that the aromatic hydrocarbon group in L is directly bonded to -OH in formula (1-1). When the aromatic hydrocarbon group in L is directly bonded to -OH in formula (1-1), it is preferred that the positions where the above-mentioned -OH and the aromatic hydrocarbon group in L are directly or indirectly bonded to the amide bond via a linking group are adjacent positions in the aromatic hydrocarbon group in L. The adjacent position means that the ring member to which one substituent is bonded and the ring member to which another substituent is bonded in the aromatic hydrocarbon group are adjacent ring members in the aromatic hydrocarbon group, and when the aromatic hydrocarbon group is a benzene ring, it means the ortho position.

[0541] Moreover, the bonding position of L to -OH in formula (1-1) is preferably a hydrocarbon group.

[0542] -OH in formula (1-1) is a hydroxyl group. Moreover, the mode in which -OH in formula (1-1) is a phenolic hydroxyl group is also a preferred mode of the present invention.

[0543] Moreover, the linking chain of the shortest path connecting the heteroatom in L to -OH in formula (1-1) is preferably formed of 2 carbon atoms.

[0544] For example, in the case of the following compound A-1, the linking chain of the shortest path connecting the heteroatom (oxygen atom) to -OH in formula (1-1) is formed of 2 carbon atoms denoted by italic numerals 1 and 2.

[0545] [Chemical Formula 41]

[0546]

[0547] Moreover, the connecting chain of the shortest path connecting the heteroatom in L to the carbonyl group in formula (1-1) is preferably formed of 1 or 2 carbon atoms, more preferably formed of 1 carbon atom. For example, the heteroatom in L and the carbonyl group in formula (1-1) are preferably connected by a methylene group or a vinyl group, more preferably connected by a methylene group.

[0548] Among these, L is preferably a group represented by a combination of an aromatic hydrocarbon group, an aliphatic hydrocarbon ring group, and a linear aliphatic saturated hydrocarbon group.

[0549] When L is a group represented by a combination of an aromatic hydrocarbon group, an aliphatic hydrocarbon ring group, and a linear aliphatic hydrocarbon group, the bonding site to -OH in formula (1-1) preferably exists in the aromatic hydrocarbon group or the aliphatic hydrocarbon ring group, and the bonding site to the carbonyl group in formula (1-1) exists in the linear aliphatic saturated hydrocarbon group.

[0550] The preferred forms of the above-mentioned aromatic hydrocarbon group, aliphatic hydrocarbon ring group, and aliphatic saturated hydrocarbon group are as described above.

[0551] Moreover, L may further contain -OH in the structure, and may further contain an amide bond (-C(=O)NR2). The above R has the same meaning as R in formula (1-1).

[0552] Moreover, from the viewpoint of further improving the rectangularity of the pattern, L preferably further contains a polymerizable group. As the polymerizable group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Examples include groups in which a vinyl group is directly bonded to an aromatic ring such as vinylphenyl, (meth)acryloyloxy group, (meth)acrylamide group, maleimide group, vinyl group, allyl group, etc., and vinylphenyl or (meth)acryloyloxy group is more preferred.

[0553] As a specific example of L, the following bases can be cited, for example, but are not limited thereto. In the following structures, * represents the bonding site to OH in formula (1-1), and # represents the bonding site to the carbonyl group in formula (1-1).

[0554] [Chemical Formula 42]

[0555]

[0556] 〔Base generator represented by formula (1-2)〕

[0557] The composition of the present invention preferably contains a base generator represented by formula (1-2) as a specific base generator.

[0558] [Chemical Formula 43]

[0559]

[0560] In formula (1-2), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs can be linked to form a ring structure. L 1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NR N -, and R N represents a hydrogen atom or a monovalent organic group, and R 1 and R 2 each independently represent a hydrogen atom or an organic group. At least two of the two Rs 1 and R 2 can combine to form a ring structure. The bond with a dashed line represents a single bond or a double bond. n represents 0 or 1. When the bond with a dashed line is a double bond, n is 1; when the bond with a dashed line is a single bond, n is 0.

[0561] -R-

[0562] In formula (1-2), R has the same meaning as R in formula (1-1), and the preferred modes are also the same.

[0563] -L 1 -

[0564] In formula (1-2), L 1 represents an alkylene group which may be substituted, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably a vinyl group.

[0565] The above-mentioned alkylene group can be any of linear, branched and cyclic, or a group represented by a combination of these, and is preferably linear or branched.

[0566] As the substituent in the above-mentioned alkylene group, as long as the effects of the present invention can be obtained, it can be used without particular limitation. For example, a carboxyl group, a halogen atom, etc. can be cited.

[0567] Moreover, the unsubstituted form of the above-mentioned alkylene group is also one of the preferred forms of the present invention.

[0568] -Z-

[0569] In formula (1-2), Z represents -O-, -S- or -NR N -, and from the viewpoint of drug resistance, -NR N - is preferred. From the viewpoint of elongation at break, -O- or -S- is preferred.

[0570] -R 1 and R 2 -

[0571] R 1 and R 2 each independently represents a hydrogen atom or an organic group, and preferably at least one is an organic group.

[0572] As R 1 , a hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group is more preferred.

[0573] As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred. Moreover, in the present invention, unless otherwise specified, the descriptions of saturated aliphatic hydrocarbon groups, alkyl groups, alkenyl groups, alkylene groups, etc. include any of linear, branched, cyclic, or structures represented by combinations thereof.

[0574] As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms can be mentioned, a group formed by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring is preferred, and a group formed by removing a plurality of hydrogen atoms from a benzene ring is more preferred.

[0575] Moreover, at least two of the two Rs 1 and R 2 can be bonded to form a ring structure, and preferably two Rs 1 are bonded to form a ring structure.

[0576] As the formed ring structure, it can be an aromatic ring structure or an aliphatic ring structure, an aromatic ring structure is preferred, an aromatic hydrocarbon ring structure is more preferred, and a benzene ring structure is particularly preferred.

[0577] For example, when two Rs 1 are bonded to form a ring structure, the bond with the dotted part in formula (1-2) is a double bond.

[0578] -n-

[0579] n represents 0 or 1, and 0 is preferred. That is, the bond with the dotted part in formula (1-2) preferably represents a double bond.

[0580] [Base generator represented by formula (1-3)]

[0581] The composition of the present invention preferably contains a base generator represented by formula (1-3) as a specific base generator.

[0582] [Chemical formula 44]

[0583]

[0584] In formula (1-3), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs can be linked to form a ring structure, L1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, and R 3 are each independently a hydrogen atom or a monovalent organic group, and at least two of R 3 may be linked to form a ring structure.

[0585] R, L in formula (1-3) 1 and the preferred forms of Z are the same as those of R, L 1 and Z in formula (1-2).

[0586] In formula (1-3), R 3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0587] Moreover, the case where R 3 is a polymerizable group such as a vinyl group is also one of the preferred forms of the present invention.

[0588] [Base generator represented by formula (1-4)]

[0589] The composition of the present invention preferably contains a base generator represented by formula (1-4) as a specific base generator. Since the base generated from formula (1-4) has a high volume around the nitrogen atom of the amino group, the reaction with the resin in the film can be inhibited by steric hindrance. As a result, the base is more easily diffused uniformly in the film. Therefore, it is considered that it is easy to suppress the difference in the film shrinkage degree between the surface side and the substrate side of the film, and the rectangularity of the obtained pattern is further excellent.

[0590] [Chemical formula 45]

[0591]

[0592] In formula (1-4), R 2 and R 4 each independently represent a monovalent organic group, and two R 2 with each other or R 2 and R 4 may be linked to form a ring structure, and L 1 represents an alkylene group which may be substituted, and Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, and R 3 are each independently a hydrogen atom or a monovalent organic group, and at least two of R 3 may be linked to form a ring structure.

[0593] Z, L in formula (1-4) 1 and R 3The preferred embodiments of Z, L in Formula (1-3) 1 and R 3 are the same as the preferred embodiments.

[0594] R in Formula (1-4) 2 has the same preferred embodiment as R in Formula (1-1). 2

[0595] R in Formula (1-4) 4 has the same preferred embodiment as R in Formula (1-1) when R is a monovalent organic group.

[0596] 〔Base〕

[0597] The specific base generator preferably exhibits the property of generating a base by heat.

[0598] That is, the specific base generator is preferably a thermal base generator.

[0599] Specifically, the specific base generator preferably generates a base by heating at 250 °C, more preferably by heating at 220 °C, further preferably exhibits the property of generating a base by heating at 200 °C, particularly preferably by heating at 190 °C, and most preferably by heating at 180 °C. The lower limit of the temperature for generating the base is not particularly limited, and from the viewpoint of the storage stability of the composition, etc., for example, it is preferably 100 °C or higher.

[0600] The following method can be used to determine whether a specific base generator exhibits the property of generating a base at a certain temperature X °C.

[0601] After heating 1 mole of the specific base generator in a sealed container under 1 atm at the above-mentioned X °C for 3 hours, the decomposition amount is quantified by methods such as NMR (nuclear magnetic resonance apparatus), HPLC (high-performance liquid chromatography), GC (gas chromatography), etc., and the case where 0.01 mole or more of the base is generated is determined as "generating a base". The amount of the generated base is preferably 0.1 mole or more, more preferably 1 mole or more. The upper limit of the amount of the generated base is not particularly limited, and for example, it can be set to 1000 moles or less.

[0602] Moreover, the molecular weight of the generated base is preferably 45 - 500, more preferably 70 - 400, and further preferably 80 - 250.

[0603] The boiling point of the generated base under 1 atm is preferably 50 - 450 °C, more preferably 60 - 400 °C, and further preferably 80 - 350 °C.

[0604] The specific base generator preferably exhibits the property of generating a base by cleavage of the amide bond described in Formula (1-1).

[0605] ​Moreover, from the viewpoint of the elongation at break of the obtained cured product, etc., the base generated from a specific base generator is preferably an amine, and more preferably a secondary amine.

[0606] Moreover, when an amine is generated from a specific resin, the amine may be an aliphatic amine or an aromatic amine.

[0607] The generated base is preferably a base having a pKa of the conjugate acid of 0 or more, more preferably 3 or more, and still more preferably 6 or more. The upper limit of the pKa of the conjugate acid is not particularly limited, and is preferably 30 or less.

[0608] pKa is the negative common logarithm pKa of the equilibrium constant Ka representing the dissociation reaction in which a hydrogen ion is released from an acid. In this specification, unless otherwise specified, pKa is set to the calculated value based on ACD / ChemSketch (registered trademark).

[0609] When there are multiple pKas of the conjugate acid, it is preferable that at least one is within the above range.

[0610] The specific example of the generated base is not particularly limited. For example, bases having the following structures can be cited.

[0611] [Chemical formula 46]

[0612]

[0613] Moreover, the dimethylpiperidine ring in the above structure has a cis form and a trans form, and either form can be used. Here, from the viewpoint of the elongation at break of the obtained cured product, the cis form is preferred.

[0614] Compared with the cis form, the volume around the nitrogen atom in the trans form becomes slightly larger. Thus, in the cis form, the matrix compound can more easily approach the nitrogen atom of the active site, and the effect of promoting imidization is improved. On the other hand, since it has a sufficiently large volume that does not react with the resin, the pattern rectangularity can be maintained. Therefore, compared with the trans form, the cis form has excellent elongation at break while maintaining other properties.

[0615] 〔Molecular weight〕

[0616] The molecular weight of the specific base generator is preferably 100 to 1,000, more preferably 100 to 800, and still more preferably 150 to 500.

[0617] If the above molecular weight is at least the above lower limit, it is easy to obtain a cured film having excellent elongation at break. Moreover, if the above molecular weight is at most the above upper limit, it is easy to suppress the film shrinkage of the cured film.

[0618] 〔Synthesis method〕

[0619] For example, a specific base generator can be synthesized by the method described in the synthesis examples in the following embodiments. Moreover, it can also be synthesized by other known synthesis methods, and the synthesis method is not particularly limited.

[0620] As a specific example of the specific base generator, there is no particular limitation, and A-1 to A-47 used in the examples can be cited. Moreover, it can also be a compound having the following structure.

[0621] [Chemical formula 47]

[0622]

[0623] The content of the specific base generator is preferably 0.5 to 20% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0624] The specific base generator 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.

[0625] Moreover, when the resin composition of the present invention contains a specific base generator and a base generator described later, the total content of the specific base generator and the base generator is preferably 0.5 to 20% by mass. The lower limit is more preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0626] <Organometallic complex>

[0627] From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex.

[0628] The organometallic complex may be an organic complex compound containing a metal atom, preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which the organic group is coordinated with the metal atom, and further preferably a metallocene compound.

[0629] In the present invention, the metallocene compound refers to an organometallic complex containing two η5-ligands of cyclopentadienyl anion derivatives which may have substituents.

[0630] As the above organic group, there is no particular limitation, and a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferred. As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferred.

[0631] In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups.

[0632] The above-mentioned cyclic group is preferably selected from cyclic groups of 5-membered rings and cyclic groups of 6-membered rings, more preferably a cyclic group of a 5-membered ring.

[0633] The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, and is preferably a hydrocarbon ring.

[0634] As the cyclic group of a 5-membered ring, cyclopentadienyl is preferred.

[0635] Moreover, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0636] The metal contained in the organometallic complex is not particularly limited, and preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from titanium, zirconium, and hafnium, still more preferably at least one metal selected from titanium and zirconium, and particularly preferably titanium.

[0637] The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, and preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom or may contain two or more kinds of metal atoms.

[0638] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0639] The mode in which the organometallic complex has the ability to initiate photo-induced radical polymerization is also one of the preferred modes of the present invention.

[0640] In the present invention, having the ability to initiate photo-induced radical polymerization means being able to generate radicals capable of initiating radical polymerization by irradiation with light. For example, when light in a wavelength region absorbed by the organometallic complex and not absorbed by the radical crosslinking agent is irradiated to a composition containing a radical crosslinking agent and an organometallic complex, the presence or absence of the ability to initiate photo-induced radical polymerization can be confirmed by confirming whether the radical crosslinking agent disappears. When confirming whether it disappears, an appropriate method can be selected according to the type of the radical crosslinking agent, and for example, it can be confirmed by IR measurement (infrared spectroscopic measurement) or HPLC measurement (high performance liquid chromatography).

[0641] When the organometallic complex has the ability to initiate photo-induced radical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0642] When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably at least one compound selected from titanocene compounds, tetraalkoxytitanium compounds, acylated titanium compounds, chelated titanium compounds, zirconocene compounds, and hafnocene compounds, more preferably at least one compound selected from titanocene compounds, zirconocene compounds, and hafnocene compounds, further preferably at least one compound selected from titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[0643] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0644] As the organometallic complex, a compound represented by the following formula (P) can be preferably selected.

[0645] [Chemical formula 48]

[0646]

[0647] In formula (P), M is a metal atom, and each R is independently a substituent.

[0648] Each of the above R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0649] In formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom, or a hafnium atom is preferred, a titanium atom, a zirconium atom, or a hafnium atom is more preferred, a titanium atom or a zirconium atom is further preferred, and a titanium atom is particularly preferred.

[0650] As the aromatic group in R in formula (P), an aromatic group having 6 to 20 carbon atoms can be mentioned, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, and examples include a phenyl group, a 1-naphthyl group, or a 2-naphthyl group.

[0651] As the alkyl group in R in formula (P), an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and examples include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group, etc.

[0652] As the halogen atom in the above R, F, Cl, Br, and I can be mentioned.

[0653] As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and examples include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group, etc.

[0654] The above R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group, etc.

[0655] Specific examples of the organometallic complex are not particularly limited, and examples thereof include titanium tetraisopropoxide, titanium tetrakis(2-ethylhexoxy), diisopropoxybis(ethyl acetoacetate)titanium, diisopropoxybis(acetylacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compound.

[0656] [Chemical formula 49]

[0657]

[0658] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 can also be used, but are not limited thereto.

[0659] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0660] One kind or two or more kinds of organometallic complexes can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0661] <Polymerizable compound>

[0662] The resin composition of the present invention preferably contains a polymerizable compound.

[0663] Examples of the polymerizable compound include a radical crosslinking agent or other crosslinking agents.

[0664] [Radical crosslinking agent]

[0665] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0666] A free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferably used. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamide.

[0667] Among these, as the group containing an ethylenically unsaturated bond, (meth)acryloyl, (meth)acrylamide, and vinylphenyl are preferred, and from the viewpoint of reactivity, (meth)acryloyl is more preferred.

[0668] The free radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The free radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0669] As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenically unsaturated bonds is further preferred.

[0670] Moreover, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably further contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds.

[0671] The molecular weight of the free 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 free radical crosslinking agent is preferably 100 or more.

[0672] As specific examples of the radically polymerizable compound, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited. Preferably, they are esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. Moreover, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as other examples, a group of compounds in which unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used instead. 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 this content is incorporated into the present specification.

[0673] Moreover, the radical crosslinking agent is also preferably a compound having a boiling point of 100 °C or higher under normal pressure. As examples thereof, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tris(acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerol or trimethylolethane and then performing (meth)acrylation, urethane (meth)acrylates described in each of Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Laid-Open No. 51-037193, polyester acrylates described in each of Japanese Patent Application Laid-Open No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Moreover, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred. Further, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group and an ethylenic unsaturated bond such as glycidyl (meth)acrylate can also be cited.

[0674] Moreover, as a preferred radical crosslinking agent other than the above, it is also possible to use compounds having a fluorene ring and containing two or more groups having an ethylenically unsaturated bond, and cardo resins described in JP-A-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216, etc.

[0675] Furthermore, as other examples, specific unsaturated compounds described in JP-B-46-043946, JP-A-01-040337, JP-A-01-040336, vinyl phosphonic acid compounds described in JP-A-02-025493, etc. can also be cited. Moreover, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

[0676] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of WO 2015 / 199219 can also be preferably used, and these contents are incorporated into this specification.

[0677] Moreover, compounds obtained by adding ethylene oxide or propylene oxide to a polyhydric alcohol and then subjecting it to (meth)acrylation, which are described as formula (1) and formula (2) together with their specific examples in JP-A-10-062986, can also be used as a radical crosslinking agent.

[0678] Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as a radical crosslinking agent, and these contents are incorporated into this specification.

[0679] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available product: 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. Oligomer types of these can also be used.

[0680] Examples of commercially available products of the radical crosslinking agent include 4-functional acrylate SR-494 having 4 ethenyloxy chains, manufactured by Sartomer Company, Inc., 2-functional methacrylate SR-209, 231, 239 having 4 ethenyloxy chains, manufactured by Sartomer Company, Inc., 6-functional acrylate DPCA-60 having 6 pentenyloxy chains, manufactured by Nippon Kayaku Co., Ltd., 3-functional acrylate TPA-330 having 3 isobutyloxy chains, urethane oligomers UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0681] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Laid-Open No. Sho 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese 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, and Japanese Patent Publication No. Hei 62-039418 are also preferred. Further, as the radical crosslinking agent, compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Laid-Open No. Sho 63-277653, Japanese Patent Laid-Open No. Sho 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 can also be used.

[0682] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. Among the radical crosslinking agents having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a radical crosslinking agent having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride is more preferred. Particularly preferred is a compound in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol among the radical crosslinking agents having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. As commercially available products, for example, polybasic acid-modified acrylic oligomers M-510, M-520, etc. manufactured by TOAGOSEI CO., LTD. can be cited.

[0683] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgK0H / g. As long as the acid value of the radical crosslinking agent is within the above range, the operability in production is excellent, and further, the developability is excellent. Moreover, the polymerizability is good. The above acid value is measured according to the description in JIS K 0070:1992.

[0684] From the viewpoints of pattern resolution and film stretchability, a bifunctional methacrylate or acrylate is preferably used in the resin composition.

[0685] 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, 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 isocyanuric acid diacrylate, modified isocyanuric acid dimethacrylate, other difunctional acrylates having a urethane bond, difunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed.

[0686] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is about 200.

[0687] From the viewpoint of suppressing warpage caused by controlling the elastic modulus 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 can be preferably used. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100 °C or higher at normal pressure is also preferred.

[0688] In addition, as the radical crosslinking agent having two or more functional groups, allyl compounds such as diallyl phthalate and triallyl trimellitate can be mentioned.

[0689] When a free radical crosslinking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0690] The free radical crosslinking agent may be used alone as one kind, or two or more kinds may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably within the above range.

[0691] 〔Other crosslinking agents〕

[0692] The resin composition of the present invention preferably further contains other crosslinking agents different from the above free radical crosslinking agent.

[0693] In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above free radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule that promote the formation of a covalent bond with other compounds or reaction products thereof in the composition by the photosensitization of a photoacid generator or a photobase generator, and more preferably a compound having a plurality of groups in the molecule that promote the formation of a covalent bond with other compounds or reaction products thereof in the composition by the action of an acid or a base.

[0694] The above acid or base is preferably an acid or a base generated from a photoacid generator or a photobase generator in the exposure step.

[0695] As the other crosslinking agent, a compound having at least one group selected from acyloxymethyl, hydroxymethyl, and alkoxymethyl is preferred, and a compound having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom is more preferred.

[0696] As the other crosslinking agent, for example, a compound having a structure obtained by reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylurea, or benzoguanamine with formaldehyde or reacting formaldehyde with an alcohol and substituting the hydrogen atom of the above amino group with acyloxymethyl, hydroxymethyl, or alkoxymethyl can be cited. The production method of these compounds is not particularly limited as long as it is a compound having the same structure as the compound produced by the above method. Moreover, it can be an oligomer formed by self-condensation of hydroxymethyl groups of these compounds.

[0697] As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea, or alkylurea is called a urea-based crosslinking agent, a crosslinking agent using alkylurea is called an alkylurea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.

[0698] Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

[0699] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, examples of the structural example include a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the following urea structure, or a triazine.

[0700] Regarding the alkoxymethyl group or acyloxymethyl group possessed by the above compound, the number of carbon atoms is preferably 2 to 5, more preferably 2 or 3, and further preferably 2.

[0701] The total number of the alkoxymethyl group and the acyloxymethyl group possessed by the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0702] The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.

[0703] [Chemical formula 50]

[0704]

[0705] R 100 represents an alkyl group or an acyl group.

[0706] R 101 and R 102 each independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0707] As the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, for example, compounds such as the following general formula can be cited.

[0708] [Chemical formula 51]

[0709]

[0710] In the formula, X represents a single bond or a divalent organic group, and each R 104 independently represents an alkyl group or an acyl group, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid and generates a base-soluble group (for example, a group that detaches by the action of an acid, a group represented by -C(R 4 )2COOR 5 represented group (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that detaches by the action of an acid. )).

[0711] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0712] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that is released by the action of an acid, and the group that is -C(R 4 )2COOR 2 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0713] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0714] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0715] The above-mentioned alkyl group may be either linear or branched.

[0716] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[0717] The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

[0718] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0719] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[0720] The above-mentioned aralkyl group means an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the above-mentioned alkyl groups and aryl groups.

[0721] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0722] Further, these groups may further have known substituents within the scope of achieving the effects of the present invention.

[0723] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0724] As the group that decomposes by the action of an acid to generate a base-soluble group or the group that detaches by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0725] As the compound having an alkoxymethyl group, the following structures can be specifically cited. As the compound having an acyloxymethyl group, a compound in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group can be cited. As the compound having an alkoxymethyl group or an acyloxymethyl group in the molecule, the following compounds can be cited, but are not limited thereto.

[0726] [Chemical formula 52]

[0727]

[0728] [Chemical formula 53]

[0729]

[0730] Regarding the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product can be used, and a compound synthesized by a known method can also be used.

[0731] From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferred.

[0732] As a specific example of the melamine-based crosslinking agent, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl butyl melamine, etc. can be cited.

[0733] As a specific example of the urea-based crosslinking agent, for example, glyoxal-based crosslinking agents such as monohydroxymethylated glyoxal, dihydroxymethylated glyoxal, trihydroxymethylated glyoxal, tetrahydroxymethylated glyoxal, monomethoxymethylated glyoxal, dimethoxymethylated glyoxal, trimethoxymethylated glyoxal, tetramethoxymethylated glyoxal, monoethoxymethylated glyoxal, diethoxymethylated glyoxal, triethoxymethylated glyoxal, tetraethoxymethylated glyoxal, monopropoxymethylated glyoxal, dipropoxymethylated glyoxal, tripropoxymethylated glyoxal, tetrapropoxymethylated glyoxal, monobutoxymethylated glyoxal, dibutoxymethylated glyoxal, tributoxymethylated glyoxal or tetrabutoxymethylated glyoxal;

[0734] Urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, dibutoxymethylurea, etc.

[0735] Ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea, etc.

[0736] Allyl urea-based crosslinking agents such as monohydroxymethylated allyl urea, dihydroxymethylated allyl urea, monomethoxymethylated allyl urea, dimethoxymethylated allyl urea, monoethoxymethylated allyl urea, diethoxymethylated allyl urea, monopropoxymethylated allyl urea, dipropoxymethylated allyl urea, monobutoxymethylated allyl urea or dibutoxymethylated allyl urea, etc.

[0737] 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0738] As specific examples of benzoguanamine-based crosslinking agents, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc. can be cited.

[0739] In addition, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, a compound in which at least one group selected from hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0740] As specific examples of such compounds, there may be mentioned benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidynetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0741] As other crosslinking agents, commercially available products can be used. As preferred commercially available products, there may be mentioned 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same hereinafter) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALACMW-100LM, NIKALAC MX-750LM (manufactured by SANWA CHEMICAL CO., LTD.), and the like.

[0742] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from epoxy compounds, oxetane compounds, and benzoxazine compounds as other crosslinking agents.

[0743] - Epoxy compounds (compounds having an epoxy group)-

[0744] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction at 200°C or lower and does not cause a dehydration reaction due to crosslinking, so film shrinkage is less likely to occur. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0745] The epoxy compound preferably contains a polyoxyethylene group. Thereby, the elastic modulus is further reduced, and warping can be suppressed. The polyoxyethylene group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

[0746] Examples of the epoxide compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, or polyol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; polysiloxanes containing epoxy groups such as polymethyl(epoxypropyl)siloxane, but are not limited thereto.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Moreover, the following compounds can also be preferably used.

[0747] [Chemical formula 54]

[0748]

[0749] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0750] In the above structure, considering both heat resistance and improvement of the elongation at break, it is preferred that n is 1 to 2 and m is 3 to 7.

[0751] - Oxetane compound (compound having an oxetanyl group) -

[0752] As the oxetane compound, compounds having two or more oxetane rings in one molecule, 3 - ethyl - 3 - hydroxymethyloxetane, 1,4 - bis{[(3 - ethyl - 3 - oxetanylmethoxy)methyl]methyl}benzene, 3 - ethyl - 3 - (2 - ethylhexylmethyl)oxetane, 1,4 - benzenedicarboxylic acid - bis[(3 - ethyl - 3 - oxetanylmethyl)ester], etc. can be cited. As a specific example, ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT - 121, OXT - 221) can be preferably used, and these can be used alone or two or more of them can be mixed.

[0753] - Benzoxazine compound (compound having a benzoxazolyl group) -

[0754] Benzoxazine compounds are preferred because they do not generate gas during curing due to the cross - linking reaction caused by ring - opening addition reaction, and further reduce thermal shrinkage to suppress warpage.

[0755] As preferred examples of the benzoxazine compound, P - d type benzoxazine, F - a type benzoxazine (the above are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resin, novolac type dihydrobenzoxazine compounds can be cited. These can be used alone or two or more of them can be mixed.

[0756] The content of other cross - linking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. Other cross - linking agents can contain only one kind or can contain two or more kinds. When two or more other thermal cross - linking agents are contained, their total is preferably within the above range.

[0757] [Polymerization initiator]

[0758] The resin composition of the present invention preferably contains a polymerization initiator capable of starting polymerization by light and / or heat. Particularly preferably, it contains a photo - polymerization initiator.

[0759] The photoinitiator is preferably a photo radical polymerization initiator. As the photo radical polymerization initiator, there is no particular limitation, 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. Moreover, it can be an active agent that generates active radicals by having some action with a photosensitizer excited by light.

[0760] The photo radical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 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, by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), preferably using ethyl acetate as the solvent, the measurement is carried out at a concentration of 0.01 g / L.

[0761] 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. For the detailed content of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Laid-Open No. 201δ-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and this content is incorporated into this specification. Moreover, compounds described in paragraphs 0065 to 0111 of Japanese Patent Laid-Open No. 2014-130173, Japanese Patent No. 6301489, peroxide-based photoinitiators described in MATERIALS 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 Laid-Open No. 2019-043864, photoinitiators described in Japanese Patent Laid-Open No. 2019-044030, peroxide-based initiators described in Japanese Patent Laid-Open No. 2019-167313, and these contents are incorporated into this specification.

[0762] As the ketone compound, for example, the compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content is incorporated into the present specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0763] In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminobenzophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminobenzophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the content is incorporated into the present specification.

[0764] As the α-hydroxy ketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all are manufactured by BASF Corporation) can be used.

[0765] As the α-amino ketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGAC URE 369, and IRGACURE379 (trade names: all are manufactured by BASF Corporation) can be used.

[0766] As the aminobenzophenone-based initiator, the compounds described in JP-A-2009-191179 whose maximum absorption wavelength matches a wavelength light source such as 365 nm or 405 nm can also be used, and the content is incorporated into the present specification.

[0767] As the acylphosphine oxide-based initiator, 2,4,6-trimethylbenzoyl-diphenyl-oxide phosphine, etc. can be mentioned. Moreover, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819, IRGACURE-TPO (trade names: all are manufactured by BASF Corporation) can be used.

[0768] Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.), and the like.

[0769] As the photo radical polymerization initiator, an oxime compound is more preferably selected. By using the oxime compound, the exposure latitude can be further effectively improved. The exposure latitude (exposure margin) of the oxime compound is wide and it also functions as a photocuring accelerator, and thus it is particularly preferred.

[0770] Specific examples of the oxime compound include the compounds described in Japanese Unexamined Patent Application Publication No. 2001-233842, the compounds described in Japanese Unexamined Patent Application Publication No. 2000-080068, the compounds described in Japanese Unexamined Patent Application Publication No. 2006-342166, the compounds described in J.C.S. Perkin II (1979, pages 1653-1660), the compounds described in J.C.S. Perkin II (1979, pages 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pages 202-232), the compounds described in Japanese Unexamined Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Laid-Open No. 2004-534797, the compounds described in Japanese Unexamined Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Unexamined Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc. The content is incorporated into this specification.

[0771] As preferred oxime compounds, 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. can be cited. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photo radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[0772] [Chemical formula 55]

[0773]

[0774] Among commercially available products, 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) can also be preferably used. Moreover, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Moreover, DFI-091 (manufactured by Daito Chemix Corporation), SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, oxime compounds having the following structures can also be used.

[0775] [Chemical formula 56]

[0776]

[0777] As the photo radical polymerization initiator, an oxime compound having a fluorene ring can also be used. As specific examples of the oxime compound having a fluorene ring, the compounds described in Japanese Unexamined Patent Application Publication No. 2014-137466 and Japanese Patent No. 06636081 are cited, and the content is incorporated into this specification.

[0778] As a photo radical polymerization initiator, an oxime compound in which at least one benzene ring having a carbazole ring forms a naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013 / 083505, the content of which is incorporated into this specification.

[0779] An oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Unexamined Patent Application Publication No. 2010-262028, the compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Laid-Open No. 2014-500852, the compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Application Publication No. 2013-164471, etc., the content of which is incorporated into this specification.

[0780] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Unexamined Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012, 0070 to 0079 of Japanese Unexamined Patent Application Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the content of which is incorporated into this specification. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) can also be mentioned.

[0781] As a photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include 0E-01 to 0E-75 described in International Publication No. 2015 / 036910.

[0782] As a photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Specific examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019 / 088055, the content of which is incorporated into this specification.

[0783] As a photopolymerization initiator, an oxime compound having an aromatic ring group Ar 0X1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. As the above aromatic ring group Ar 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, and a benzoyl group is further preferred. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxy 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, or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or an amino group is more preferred; and an alkoxy group, an alkylthio group, or an amino group is further preferred.

[0784] 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).

[0785] [Chemical formula 57]

[0786]

[0787] 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,

[0788] 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,

[0789] R X3 ~R X14 each independently represents a hydrogen atom or a substituent.

[0790] Among them, at least one of R X10 ~R X14 is an electron-withdrawing group.

[0791] In the above formula, preferably, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 are hydrogen atoms.

[0792] 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.

[0793] As the most preferred oxime compound, an oxime compound having a specific substituent shown in JP-A-2007-269779, an oxime compound having a thioaryl group shown in JP-A-2009-191061, etc. may be mentioned, and the content is incorporated into this specification.

[0794] From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound 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, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds.

[0795] More preferred photo radical polymerization initiators are trihalomethyltriazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, and still 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 further preferably a metallocene compound or an oxime compound is used.

[0796] Moreover, as the photo radical polymerization initiator, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, quinones formed by condensing aromatic rings such as alkyl anthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoins, benzyl derivatives such as benzyldimethyl ketal, etc. can also be used. Moreover, a compound represented by the following formula (I) can also be used.

[0797] [Chemical formula 58]

[0798]

[0799] In formula (I), R I00is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or biphenyl group substituted by at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by the formula (II) or the same group as R I00 and R I02 to R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0800] [Chemical formula 59]

[0801]

[0802] In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

[0803] Furthermore, as the photo radical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and this content is incorporated into the present specification.

[0804] As the photo radical polymerization initiator, a bifunctional or polyfunctional photo radical initiator having 3 or more functions can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like becomes high, and precipitation hardly occurs over time, whereby the stability over time of the resin composition can be improved. Specific examples of the bifunctional or polyfunctional photo radical polymerization initiator include the dimers of oxime compounds 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, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, the compounds (E) and (G) described in Japanese Patent Application Laid-Open No. 2013-522445, Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Application Laid-Open No. 2017-523465, the photoinitiators 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., and this content is incorporated into the present specification.

[0805] When the photopolymerization initiator is contained, 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 relative to the total solid content of the resin composition of the present invention. The photopolymerization initiator may contain only 1 type or may contain 2 or more types. When 2 or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0806] In addition, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator, and thus crosslinking based on the photopolymerization initiator is sometimes further promoted by heating with an oven, a hot plate or the like.

[0807] 〔Sensitizer〕

[0808] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator or the like to cause effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and decompose, and radicals, acids or bases are generated.

[0809] As sensitizers that can be used, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxacyanine-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.

[0810] 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-dimethylaminobenzylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isoindolylthiazole, 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.

[0811] Moreover, sensitizing dyes can also be used.

[0812] Regarding the detailed content of the sensitizing dyes, reference can be made to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification.

[0813] 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.

[0814] 〔Chain transfer agent〕

[0815] 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 Third Edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, compounds having -S-S-, -SO2-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. can be used. These generate radicals by supplying hydrogen to low-reactivity radicals or can generate radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

[0816] Moreover, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used as the chain transfer agent, and this content is incorporated into this specification.

[0817] When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, their total is preferably within the above range.

[0818] <Base generator>

[0819] 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 the base generator preferred for the resin composition of the present invention, a thermal base generator and a photo base generator can be cited.

[0820] Among them, the base generator corresponding to the above specific base generator is not the base generator referred to in the present invention.

[0821] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, so that the mechanical properties and chemical resistance of the cured product are improved. For example, the performance of the interlayer insulating film for the rewiring layer included in the semiconductor package is improved.

[0822] As the base generator, an ionic base generator or a nonionic base generator can be used. Examples of the base generated from the base generator include secondary amines and tertiary amines.

[0823] The base generator of the present invention 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, urethane compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminobenzeneacetone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxy imide compounds, etc. can be used.

[0824] Specific compounds of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

[0825] [Chemical formula 60]

[0826]

[0827] In formula (R1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. Among them, Rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Moreover, Rb 1 , Rb 2 and Rb 3 all do not have a carboxyl group. In addition, in the present specification, the tertiary amine structure means a structure in which the three bonding bonds of the trivalent nitrogen atom are all covalently bonded to hydrocarbon-based carbon atoms. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, it is not limited thereto.

[0828] In formula (B1) and (B2), preferably Rb 1 , Rb 2 and Rb 3At least one of them contains a cyclic structure, and more preferably at least two contain a cyclic structure. As the cyclic structure, it can be either a monocyclic ring or a fused ring, preferably a monocyclic ring or a fused ring formed by condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0829] More specifically, Rb 1 and Rb 2 are preferably a hydrogen atom, an alkyl group (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (the number of carbon atoms is preferably 2 to 24, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (the number of carbon atoms is preferably 7 to 25, more preferably 7 to 19, and further preferably 7 to 12). These groups may have substituents within the range where the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. As the formed ring, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. In particular, Rb 1 and Rb 2 are preferably a straight-chain, branched-chain or cyclic alkyl group (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12) which may have substituents, more preferably a cycloalkyl group (the number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, and further preferably 3 to 12) which may have substituents, and further preferably a cyclohexyl group which may have substituents.

[0830] As Rb 3 , examples include an alkyl group (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10), an alkenyl group (the number of carbon atoms is preferably 2 to 24, more preferably 2 to 12, and further preferably 2 to 6), an aralkyl group (the number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 12), an aralkenyl group (the number of carbon atoms is preferably 8 to 24, more preferably 8 to 20, and further preferably 8 to 16), an alkoxy group (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12), an aryloxy group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyloxy group (the number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 12). Among them, a cycloalkyl group (the number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, and further preferably 3 to 12), an aralkenyl group, and an aralkyloxy group are preferred. Rb 3 may further have substituents within the range where the effects of the present invention are exhibited.

[0831] The compound represented by the formula (R1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0832] [Chemical formula 61]

[0833]

[0834] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rbw and Rb in the formula (B1). 2 have the same meanings.

[0835] Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and may have substituents within the scope of exerting the effects of the present invention. Among them, Rb 13 is preferably an aralkyl group.

[0836] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0837] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and an aryl group is preferred.

[0838] The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1a).

[0839] [Chemical formula 62]

[0840]

[0841] Rh 11 and Rb 12 and the Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0842] Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group.

[0843] Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and preferably an aryl group.

[0844] [Chemical formula 63]

[0845]

[0846] In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. Moreover, R N1 and R N2 each independently represent a monovalent organic group.

[0847] In this specification, the "linking chain" means an atomic chain on the path connecting two atoms or atomic groups to be linked, and is a chain that connects these linking objects at the shortest (minimum number of atoms) distance. For example, in the compound represented by the following formula, L is composed of styrene, has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter, also referred to as "linking chain length" or "length of the linking chain") is 4.

[0848] [Chemical formula 64]

[0849]

[0850] The number of carbon atoms in L in formula (B3) (including also the carbon atoms other than those in the linking chain) is preferably from 3 to 24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of allowing the above-mentioned intramolecular cyclization reaction to proceed rapidly, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less. The linking chain length of L is particularly preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds as the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0851] Furthermore, the base generator preferably contains a compound represented by the following formula (N1).

[0852] [Chemical formula 65]

[0853]

[0854] In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0855] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As the upper limit, it is preferably 12 or less, more preferably 8 or less, still more preferably 5 or less. The linking chain length means the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0856] In formula (N1), R N1 and R N2 each independently represent a monovalent organic group (the number of carbon atoms is preferably from 1 to 24, more preferably from 2 to 18, still more preferably from 3 to 12), preferably a hydrocarbon group (the number of carbon atoms is preferably from 1 to 24, more preferably from 1 to 12, still more preferably from 1 to 10). Specifically, an aliphatic hydrocarbon group (the number of carbon atoms is preferably from 1 to 24, more preferably from 1 to 12, still more preferably from 1 to 10) or an aromatic hydrocarbon group (the number of carbon atoms is preferably from 6 to 22, more preferably from 6 to 18, still more preferably from 6 to 10) can be cited, and an aliphatic hydrocarbon group is preferred. As R N1 and R N2, if an aliphatic hydrocarbon group is used, the resulting base has a high basicity and is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have substituents, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may also have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, a mode in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

[0857] As the aliphatic hydrocarbon group constituting R N1 and R N2 , there can be mentioned a linear or branched chain alkyl group, a cyclic alkyl group, a group involving a combination of a linear or branched chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms of the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. For example, the linear or branched chain alkyl group can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc.

[0858] The number of carbon atoms of the cyclic alkyl group is preferably 3 to 12, and more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.

[0859] The number of carbon atoms of the group involving a combination of a linear or branched chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group involving a combination of a linear or branched chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, ethylcyclohexylethyl, etc.

[0860] The number of carbon atoms of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group having an oxygen atom in the chain can be linear or cyclic, and can also be linear or branched.

[0861] Among them, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 are preferably alkyl groups having 5 to 12 carbon atoms. Among them, in a formulation that emphasizes the adhesion when laminated with a metal (such as copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0862] R N1 and R N2 can be linked to each other to form a cyclic structure. When forming a cyclic structure, an oxygen atom or the like can be present in the chain. Moreover, R N1 and R N2The formed cyclic structure may be a single ring or a fused ring, preferably a single ring. As the formed cyclic structure, a 5-membered ring or a 6-membered ring containing the nitrogen atom in the formula (N1) is preferred. For example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. can be cited. Preferably, a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring can be selected.

[0863] R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0864] As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid can be preferably selected.

[0865] Specific examples of the protecting group include a linear or cyclic alkyl group or a linear or cyclic alkyl group having an oxygen atom in the chain. As the linear or cyclic alkyl group, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. Specifically, as the linear alkyl group having an oxygen atom in the chain, an alkoxyalkyl group can be cited. More specifically, methoxymethyl (MOM), ethoxyethyl (EE), etc. can be cited. As the cyclic alkyl group having an oxygen atom in the chain, an epoxy group, an epoxypropyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. can be cited.

[0866] The divalent linking group constituting L is not particularly limited, and a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have a substituent, and may also have an atom other than a carbon atom in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, or a group involving a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain is more preferred, and a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain is further preferred. These groups preferably do not have an oxygen atom.

[0867] The number of carbon atoms of the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and further preferably 2 to 6. The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. The number of carbon atoms of the group involving a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, arylalkyl) is preferably 7 to 22, more preferably 7 to 18, and further preferably 7 to 10.

[0868] As the linking group L, specifically, groups involving linear or branched chain-like alkylene groups, cycloalkylene groups, combinations of chain-like alkylene groups and cycloalkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain-like alkenylene groups, cycloalkenylene groups, arylene groups, and arylalkylene groups are preferred.

[0869] The number of carbon atoms of the linear or branched chain-like alkylene group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

[0870] The number of carbon atoms of the cycloalkylene group is preferably 3 to 12, more preferably 3 to 6.

[0871] The number of carbon atoms of the group involving the combination of a chain-like alkylene group and a cycloalkylene group is preferably 4 to 24, more preferably 4 to 12, and still more preferably 4 to 6.

[0872] The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may also be linear or branched. The number of carbon atoms of the alkylene group having an oxygen atom in the chain is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3.

[0873] The number of carbon atoms of the linear or branched chain-like alkenylene group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 3. The number of C═C bonds of the linear or branched chain-like alkenylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.

[0874] The number of carbon atoms of the cycloalkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of C═C bonds of the cycloalkenylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.

[0875] The number of carbon atoms of the arylene group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10.

[0876] The number of carbon atoms of the arylalkylene group is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11.

[0877] Among them, chain-like alkylene groups, cycloalkylene groups, alkylene groups having an oxygen atom in the chain, chain-like alkenylene groups, arylene groups, and arylalkylene groups are preferred, and 1,2-ethenyl, propane-1,3-diyl (especially 1,3-propane-1,3-diyl), cyclohexane-1,2-diyl (especially 1,2-cyclohexane-1,2-diyl), ethenylene (especially cis-ethenylene), phenylene (1,2-phenylene), phenylmethylene (especially 1,2-phenylmethylene), ethenoxyethenyl (especially 1,2-ethenoxy-1,2-ethenyl) are more preferred.

[0878] Examples of the base generator are shown below, but the present invention should not be construed as being limited thereto.

[0879] [Chemical Formula 66]

[0880]

[0881] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0882] As specific examples of the preferred compounds of the ionic base generator, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002 can also be cited.

[0883] As specific examples of the ammonium salts, the following compounds can be cited, but the present invention is not limited thereto.

[0884] [Chemical Formula 67]

[0885]

[0886] As specific examples of the imine salts, the following compounds can be cited, but the present invention is not limited thereto.

[0887] [Chemical Formula 68]

[0888]

[0889] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still further preferably 10 parts by mass or less, can be 5 parts by mass or less, and can also be 4 parts by mass or less.

[0890] One or two or more kinds of base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0891] <Solvent>

[0892] The resin composition of the present invention preferably contains a solvent.

[0893] As the solvent, known solvents can be arbitrarily used. The solvent is preferably an organic solvent. As the organic solvent, compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols can be cited.

[0894] As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl 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. can be preferably selected.

[0895] As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. can be preferably selected.

[0896] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. can be preferably selected.

[0897] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., and cyclic terpenes such as limonene can be preferably selected.

[0898] As sulfoxides, for example, dimethyl sulfoxide can be preferably selected.

[0899] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-formylmorpholine, N-acetylmorpholine, etc. can be preferably selected.

[0900] As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. can be preferably selected.

[0901] As alcohols, 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, diacetone alcohol, etc. can be cited.

[0902] Regarding the solvent, from the viewpoint of improving the coating surface properties, etc., a method of mixing two or more kinds is also preferred.

[0903] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferably used. Particularly preferably, dimethyl sulfoxide and γ-butyrolactone are used in combination or N-methyl-2-pyrrolidone and ethyl lactate are used in combination.

[0904] Regarding the content of the solvent, from the viewpoint of coatability, it 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 such that the total solid content concentration becomes 5 to 75% by mass, further preferably set to an amount such that the total solid content concentration becomes 10 to 70% by mass, and even more preferably set to an amount such that the total solid content concentration becomes 20 to 70%. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

[0905] The resin composition of the present invention may contain only one kind of solvent or may contain two or more kinds. When two or more kinds of solvents are contained, their total is preferably within the above range.

[0906] <Metal adhesion improver>

[0907] The resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used in electrodes, wirings, etc. As the metal adhesion improver, examples 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.

[0908] [Silane coupling agent]

[0909] As the silane coupling agent, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are cited, and these are incorporated into this 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. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Me represents methyl and Et represents ethyl.

[0910] [Chemical formula 69]

[0911]

[0912] 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-(trimethoxysilylpropyl)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.

[0913]

[0914] As aluminum-based adhesion aids, for example, aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), aluminum diisopropyl ester ethyl acetoacetate, etc. can be cited.

[0915] Moreover, 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.

[0916] The content of the metal adhesion improver is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. 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. When using two or more kinds, their total is preferably within the above range.

[0917]

[0918] ​​The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, it is possible to effectively inhibit the transfer of metal ions derived from a metal layer (metal wiring) into the film.

[0919] 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 compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0920] Alternatively, an ion scavenger that scavenges anions such as halogen ions can also be used.

[0921] As other migration inhibitors, rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219 can be used, and these are incorporated into the present specification.

[0922] Specific examples of the migration inhibitor include the following compounds.

[0923] [Chemical formula 70]

[0924]

[0925] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition of the present invention.

[0926] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, their total is preferably within the above range.

[0927] <Polymerization inhibitor>

[0928] 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-oxy radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, metal compounds, and the like.

[0929] As specific compounds of the polymerization inhibitor, hydroquinone, catechol, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic acid, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), cerous N-nitrosophenylhydroxylamine salt, aluminum N-nitrosophenylhydroxylamine salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, ammonium N-nitroso-N-(1-naphthyl)hydroxylamine, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbamate, nitrobenzene, aluminum N-nitrosophenylhydroxylamine salt, ammonium N-nitrosophenylhydroxylamine salt, etc. can be preferably used. Moreover, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015 / 125469 can also be used, and the content is incorporated into this specification.

[0930] When the resin composition of the present invention has 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 of the present invention.

[0931] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, their total amount is preferably within the above range.

[0932] <Other additives>

[0933] The resin composition of the present invention can be blended with various additives as needed within the range of achieving the effects of the present invention. For example, photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, antiagglomerants, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (such as defoamers, flame retardants, etc.) that are well known in the art. By appropriately containing these components, properties such as film properties can be adjusted. Regarding these components, for example, the descriptions from paragraph 0183 onwards of Japanese Patent Application Laid-Open No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812) and paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Laid-Open No. 2008-250074, etc. can be referred to, and these contents are incorporated into this specification. When blending these additives, the total blending amount is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0934] 〔Surfactant〕

[0935] As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0936] By containing a surfactant in the photosensitive resin composition of the present invention, the liquid characteristics (especially fluidity) when preparing the coating solution can be further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when forming a film using a composition containing a surfactant, the interfacial tension between the coated surface and the coating solution decreases, thereby improving the wettability of the coated surface and enhancing the coatability on the coated surface. Therefore, a film with uniform thickness and small thickness unevenness can be formed more preferably.

[0937] As fluorosurfactants, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorosurfactants can also use the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503, and these contents are incorporated into this specification. As fluorosurfactants, block polymers can also be used. As specific examples, for example, the compounds described in Japanese Patent Application Laid-Open No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0938] Fluorosurfactants can also preferably use fluorine-containing polymer compounds (including repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group)), and the following compounds can also be exemplified as the fluorosurfactants used in the present invention.

[0939] [Chemical formula 71]

[0940]

[0941] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0942] Regarding the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Unexamined Patent Application Publication No. 2010-164965 are cited, and this content is incorporated into the present specification. Moreover, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation can be cited.

[0943] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of the thickness uniformity and liquid-saving property of the coating film, and has good solubility in the composition.

[0944] Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

[0945] As hydrocarbon surfactants, for example, PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T (manufactured by TAKEMOTO OIL&FAT CO., LTD.) etc. can be cited.

[0946] As nonionic surfactants, glycerin, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin ethoxylate etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester etc. can be exemplified. As commercially available products, PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., Ltd.) etc. can be cited.

[0947] As cationic surfactants, specifically, silicone polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymers POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoeisha chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) etc. can be cited.

[0948] As an anionic surfactant, specifically, W004, W005, W017 (Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), etc. can be mentioned.

[0949] The surfactant may be used alone or in combination of two or more.

[0950] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0951] [Higher fatty acid derivatives]

[0952] In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanamide can be added to the resin composition of the present invention so that they are biased on the surface of the resin composition of the present invention during the drying process after coating.

[0953] Moreover, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0954] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. The higher fatty acid derivatives may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, their total is preferably within the above range.

[0955] [Thermal polymerization initiator]

[0956] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be promoted, and thus the solvent resistance can be further improved. Moreover, sometimes the above-mentioned photoinitiator also has a function of starting polymerization by heat, and thus can sometimes be added as a thermal polymerization initiator.

[0957] As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554 can be mentioned, and this content is incorporated into this specification.

[0958] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may contain only one kind or may contain two or more kinds. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0959] 〔Inorganic particles〕

[0960] The resin composition of the present invention may contain inorganic particles. Specifically, as the inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be contained.

[0961] As the average particle diameter of the above inorganic particles, 0.01 to 2.0 μm is preferred, 0.02 to 1.5 μm is more preferred, 0.03 to 1.0 μm is still more preferred, and 0.04 to 0.5 μm is particularly preferred.

[0962] 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 by the dynamic light scattering method of Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0963] When 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.

[0964] 〔Ultraviolet absorber〕

[0965] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based can be used.

[0966] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, etc. Moreover, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0967] Examples of the acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, examples of the triazine-based ultraviolet absorbers include mono( hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; bis( hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris( hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, and the like.

[0968] In the present invention, the above various ultraviolet absorbers may be used alone or in combination of two or more.

[0969] The composition of the present invention may or may not contain an ultraviolet absorber. When it contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[0970] [Organic titanium compound]

[0971] The resin composition of the present embodiment may contain an organic titanium compound. By containing an organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0972] Examples of the organic titanium compounds that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0973] Specific examples of the organic titanium compounds are shown in the following I) to VII).

[0974] I) Chelated titanium compounds: Among them, from the aspects of excellent storage stability of the resin composition and good cured patterns, chelated titanium compounds having two or more alkoxy groups are more preferred. Specific examples are bis(triethanolamine)diisopropoxytitanium, di(n-butoxy)bis(2,4-pentanedioate)titanium, diisopropoxybis(2,4-pentanedioate)titanium, diisopropoxybis(tetramethylheptanedioate)titanium, diisopropoxybis(ethyl acetoacetate)titanium, etc.

[0975] II) Tetraalkoxytitanium compounds: For example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexoxy)titanium, tetra(isobutoxy)titanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0976] III) Titanocene compounds: For example, pentamethylcyclopentadienyltrimethoxytitanium, 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.

[0977] IV) Monoalkoxytitanium compounds: For example, isopropoxytitanium tris(dioctyl phosphate), isopropoxytitanium tris(dodecyl benzenesulfonate), etc.

[0978] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedioate), titanium oxide bis(tetramethylheptanedioate), titanium oxide phthalocyanine, etc.

[0979] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

[0980] VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0981] Among them, as the organotitanium compounds, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the above I) chelated titanium compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds is preferred. Diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0982] When the organotitanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0983] 〔Antioxidant〕

[0984] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the tensile properties of the cured film and the adhesion to metal materials can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, thioether compounds, etc. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. A compound having a substituent at a position (ortho position) adjacent to the phenolic hydroxyl group is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Moreover, the antioxidant preferably has a compound having a phenol group and a phosphite group in the same molecule. Moreover, a phosphorus-based antioxidant can also be preferably used as the antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, etc. Examples of commercially available products of the antioxidant include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION), etc. Moreover, the compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant, and the content is incorporated into this specification. Moreover, the composition of the present invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include a compound in which a site that functions as an antioxidant is protected by a protecting group, and in this compound, the protecting group is removed by heating at 100 to 250 °C or heating at 80 to 200 °C in the presence of an acid / base catalyst to function as an antioxidant. Examples of the latent antioxidant include the compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Unexamined Patent Application Publication No. 2017-008219, and the content is incorporated into this specification. Examples of commercially available products of the latent antioxidant include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION), etc.

[0985] Examples of preferred antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and the compound represented by formula (3).

[0986] [Chemical formula 72]

[0987]

[0988] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R 7 represents a 1- to 4-valent organic group containing at least any of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0989] The compound represented by formula (3) inhibits the oxidative degradation of aliphatic groups and phenolic hydroxyl groups possessed by the resin. Moreover, by the rust prevention effect on metal materials, metal oxidation can be inhibited.

[0990] In order to act on both the resin and the metal material, k is more preferably an integer of 2 to 4. As R 7 , examples include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, groups formed by combining these, etc., and may further have substituents. Among them, from the viewpoints of solubility in the developer and metal adhesion, an alkyl ether and -NH- are preferred, and -NH- is more preferred from the viewpoints of interaction with the resin and metal adhesion based on metal complex formation.

[0991] Examples of the compound represented by general formula (3) include the following compounds, but are not limited to the following structures.

[0992] [Chemical formula 73]

[0993]

[0994] [Chemical formula 74]

[0995]

[0996] [Chemical formula 75]

[0997]

[0998] [Chemical formula 76]

[0999]

[1000] The addition amount of the antioxidant relative to the resin 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, even in a high-temperature and high-humidity environment, it is easy to obtain the effects of tensile properties and improved adhesion to metal materials. Moreover, by setting it to 10 parts by mass or less, for example, due to the interaction with the photosensitizer, the sensitivity of the resin composition is improved. The antioxidant can be used alone or in combination of two or more. When using two or more, the total amount thereof is preferably within the above range.

[1001] 〔Anti-coagulant〕

[1002] The resin composition of the present embodiment may contain an anti-coagulant as needed. Examples of the anti-coagulant include sodium polyacrylate and the like.

[1003] In the present invention, one kind of anti-coagulant can be used alone, or two or more kinds can be used in combination.

[1004] The composition of the present invention may or may not contain an anti-coagulant. However, when contained, the content of the anti-coagulant is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[1005] 〔Phenolic compound〕

[1006] The resin composition of the present embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

[1007] In the present invention, one kind of phenolic compound can be used alone, or two or more kinds can be used in combination.

[1008] The composition of the present invention may or may not contain phenolic compounds. When contained, the content of the phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the mass of the total solid components of the composition of the present invention.

[1009] 〔Other polymer compounds〕

[1010] Examples of other polymer compounds include silicone resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

[1011] In the present invention, one kind of other polymer compound may be used alone, or two or more kinds may be used in combination.

[1012] The composition of the present invention may or may not contain other polymer compounds. When contained, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the mass of the total solid components of the composition of the present invention.

[1013] <Properties of the resin composition>

[1014] The viscosity of the resin composition of the present invention can be adjusted by the solid component 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 the insulating film for rewiring. If it is 12,000 mm 2 / s or less, a coating film with excellent coating surface condition can be obtained.

[1015] <Restrictions on substances contained in the resin composition>

[1016] 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.

[1017] As a method for maintaining the water content, methods such as humidity adjustment in storage conditions and reduction of the porosity of the storage container during storage can be cited.

[1018] From the viewpoint of insulation properties, 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 still more 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 metal complexes of organic compounds. When multiple metals are included, the total of these metals is preferably within the above range.

[1019] Moreover, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, methods such as 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 can be cited.

[1020] Regarding the resin composition of the present invention, when 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 content present in the state of halogen ions is 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 the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chloride ion and the bromine ion is preferably within the above range, respectively.

[1021] As a method for adjusting the content of halogen atoms, ion exchange treatment, etc. can be preferably cited.

[1022] As a storage container for the resin composition of the present invention, conventionally known storage containers can be used. Moreover, as the storage container, for the purpose of suppressing the mixing of impurities into the raw material or the resin composition of the present invention, a multilayer bottle having a container inner wall composed of six types of six layers of resin or a bottle having a seven-layer structure formed of six types of resin is also preferably used. As such a container, for example, the container described in Japanese Patent Application Laid-Open No. 2015-123351 can be cited.

[1023] <Cured product of the resin composition>

[1024] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1025] The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

[1026] The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and it 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. Moreover, by patterning 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 a 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.

[1027] The shrinkage rate during the curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after the curing of the resin composition, and can be calculated according to the following formula.

[1028] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[1029] <Properties of the cured product of the resin composition>

[1030] 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 further preferably 90% or more. If it is 70% or more, the cured product sometimes has excellent mechanical properties.

[1031] 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 further preferably 50% or more.

[1032] The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and further preferably 230°C or more.

[1033] <Preparation of the resin composition>

[1034] 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 it can be carried out by a conventionally well-known method.

[1035] Mixing can be carried out by mixing based on a stirring blade, mixing based on a ball mill, mixing by rotating the tank itself, etc.

[1036] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[1037] Moreover, for the purpose of removing foreign matters such as dust or fine particles from the resin composition of the present invention, it is preferable to use a filter for filtration. Regarding the pore size of the filter, for example, a method with a pore size of 5 μm or less can be cited, preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is polytetrafluoroethylene, preferably polyethylene or nylon. When the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferable. A filter that has been pre-cleaned with an organic solvent can be used. In the filtration process of the filter, multiple filters can be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, the following method can be cited: an HDPE filter with a pore size of 1 μm is used as the first stage, an HDPE filter with a pore size of 0.2 μm is used as the second stage, and the two are connected in series. Moreover, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Moreover, pressure filtration can be performed. When performing pressure filtration, for example, a method in which the applied pressure is 0.01 MPa or more and 1.0 MPa or less can be cited, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and further preferably 0.05 MPa or more and 0.5 MPa or less.

[1038] In addition to using a filter for filtration, an adsorbent material can also be used for impurity removal treatment. The filter filtration and the 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.

[1039] After filtration with a filter, a step of degassing the resin composition filled in the bottle under reduced pressure can be further performed.

[1040] (Method for manufacturing a cured product)

[1041] The method for manufacturing a cured product of the present invention preferably includes a film-forming step of applying the resin composition on a substrate to form a film.

[1042] Moreover, the method for manufacturing a cured product of the present invention 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 with a developer to form a pattern.

[1043] The method for manufacturing a cured product of the present invention 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-development exposure step of exposing the pattern obtained by the development step.

[1044] Moreover, the manufacturing method of the present invention preferably includes the above-described film-forming step and the step of heating the film.

[1045] Hereinafter, the detailed content of each step will be described.

[1046] <Film-forming step>

[1047] The resin composition of the present invention can be used in a film-forming step of forming a film by applying it to a substrate.

[1048] The manufacturing method of the cured product of the present invention preferably includes a film-forming step of applying a resin composition to a substrate to form a film.

[1049] 〔Substrate〕

[1050] The type of the substrate can be appropriately determined according to the use, and examples thereof include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, and metal substrates such as Ni, Cu, Cr, and Fe (for example, either a substrate formed of a metal or a substrate having a metal layer formed by plating, deposition, etc.). There is no particular limitation. In the present invention, a semiconductor substrate is particularly preferably used, and a silicon substrate, a Cu substrate, and a mold substrate are more preferably used.

[1051] Moreover, a bonding layer, an oxide layer, or the like formed of hexamethyldisilazane (HMDS) or the like can be provided on the surface of these substrates.

[1052] Moreover, the shape of the substrate is not particularly limited and can be a circular shape or a rectangular shape.

[1053] As the size of the substrate, if it is a circular shape, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

[1054] Moreover, as the substrate, for example, a plate shape can be used, and a panel-shaped substrate (substrate) is preferably used.

[1055] Moreover, when a resin composition is applied to the surface of a resin layer (for example, a layer composed of a cured product) or a metal layer to form a film, the resin layer or the metal layer becomes the substrate.

[1056] As a method of applying the resin composition of the present invention to the substrate, coating is preferred.

[1057] As an applicable method, specifically, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spraying, spin coating, slot coating, inkjet printing, etc. can be exemplified. From the viewpoint of the uniformity of the film thickness, spin coating, slot coating, spraying, or inkjet printing is more preferable, and from the viewpoints of the uniformity of the film thickness and productivity, spin coating and slot coating are preferable. By adjusting the solid content concentration and coating conditions of the resin composition according to the method, a film with a desired thickness can be obtained. Moreover, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating, spraying, inkjet printing, etc. are preferable, and for a rectangular substrate, slot coating, spraying, inkjet printing, etc. are preferable. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[1058] Moreover, a method of transferring a coating film formed by being previously applied to a temporary support by the above-described application method onto a substrate can also be applied.

[1059] Regarding the transfer method, in the present invention, the production methods described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used.

[1060] Moreover, a step of removing excess film at the end of the substrate can also be performed. Examples of such steps include edge bead rinse (EBR), backside rinse, etc.

[1061] Moreover, a pre-wetting step can also be employed: before coating the resin composition on the substrate, various solvents are coated on the substrate to improve the wettability of the substrate, and then the resin composition is coated.

[1062] <Drying step> ...

Claims

1. A resin composition comprising a resin and a base generator represented by the following formula (1-2), In formula (1-2), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both of the two Rs are hydrogen atoms. Optionally, the two Rs are connected to form a ring structure, and L 1 represents an optionally substituted alkylene group, Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, R 1 and R 2 each independently represent a hydrogen atom or an organic group. Optionally, at least two of the two Rs 1 and R 2 are combined to form a ring structure. The bond with a dashed line represents a single bond or a double bond. n represents 0 or 1. When the bond with a dashed line is a double bond, n is 0. When the bond with a dashed line is a single bond, n is 1. wherein the resin is at least one resin selected from a cyclized resin and a precursor of a cyclized resin.

2. The resin composition according to claim 1, comprising a compound represented by the following formula (1-3) as the base generator, In formula (1-3), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Optionally, two Rs are connected to form a ring structure. L 1 represents an optionally substituted alkylene group, and Z represents -O-, -S- or -NR N -, where R N represents a hydrogen atom or a monovalent organic group, and each R 3 is independently a hydrogen atom or a monovalent organic group. Optionally, at least two of the Rs 3 are connected to form a ring structure.

3. The resin composition according to claim 1 or 2, comprising a compound represented by the following formula (1-4) as the base generator, In formula (1-4), R 2 and R 4 each independently represent a monovalent organic group, and two Rs 2 optionally bond to each other or an R 2 bonds to an R 4 to optionally form a ring structure. L 1 represents an optionally substituted alkylene group, Z represents -O-, -S- or -NR N -, R N represents a hydrogen atom or a monovalent organic group, and Rs 3 each independently are a hydrogen atom or a monovalent organic group, and at least two of the optionally Rs 3 bond to form a ring structure.

4. The resin composition according to claim 1 or 2, wherein, the resin is a precursor of a cyclized resin.

5. The resin composition according to claim 1 or 2, further comprising a photoinitiator.

6. The resin composition according to claim 1 or 2, further comprising a polymerizable compound.

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

8. A cured product obtained by curing the resin composition according to any one of claims 1 to 7.

9. A laminate comprising two or more layers made of the cured product according to claim 8, and a metal layer is provided between any two layers made of the cured product.

10. A method for manufacturing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 7 on a substrate to form a film.

11. The method for manufacturing a cured product according to claim 10, comprising: an exposure step of selectively exposing the film; and a development step of developing the film with a developer to form a pattern.

12. The method for manufacturing a cured product according to claim 10, comprising a heating step of heating the film at 50°C to 450°C.

13. A semiconductor device comprising the cured product according to claim 8 or the laminate according to claim 9.

14. A base generator represented by the following formula (1-2), In formula (1-2), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs are optionally linked to form a ring structure. L 1 represents an optionally substituted alkylene group, and Z represents -O-, -S- or -NR N -, where R N represents a hydrogen atom or a monovalent organic group, and R 1 and R 2 each independently represent a hydrogen atom or an organic group. Optionally, at least two of the two Rs 1 and R 2 are combined to form a ring structure. The bond with the dashed line represents a single bond or a double bond. n represents 0 or 1. When the bond with the dashed line is a double bond, n is 0; when the bond with the dashed line is a single bond, n is 1.

15. The base generator according to claim 14, which is represented by the following formula (1-3), In formula (1-3), each R is independently a hydrogen atom or an arbitrary monovalent organic group, and there is no case where both Rs are hydrogen atoms. Two Rs are optionally linked to form a ring structure, and L 1 represents an optionally substituted alkylene group, and Z represents -O-, -S- or -NR N -, where R N represents a hydrogen atom or a monovalent organic group, and each R 3 is independently a hydrogen atom or a monovalent organic group. Optionally, at least two of the Rs 3 are linked to form a ring structure.

16. The base generator according to claim 14 or 15, which is represented by the following formula (1-4), In formula (1-4), R 2 and R 4 each independently represent a monovalent organic group, and two Rs 2 optionally link to each other or R 2 links to R 4 to optionally form a ring structure, L 1 represents an optionally substituted alkylene group, Z represents -O-, -S- or -NR N (-), R N represents a hydrogen atom or a monovalent organic group, and Rs 3 each independently are a hydrogen atom or a monovalent organic group, and at least two of the optionally Rs 3 link to form a ring structure.

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