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

Abstract

The present invention provides a resin composition, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate. The resin composition contains a cyclized resin or a precursor thereof and a nitrogen-containing compound. The nitrogen-containing compound contains a nitrogen-containing heterocycle and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

Description

Technical Field

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

[0002] Cyclized resins such as polyimide have excellent heat resistance and insulation properties, and are therefore suitable for various uses. The above uses are not particularly limited, but if a semiconductor device for mounting is taken as an example, the use as a material for an insulating film or a sealant or a protective film can be cited. In addition, it can also be used as a base film or cover film of a flexible substrate.

[0003] For example, in the above-mentioned application, the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin.

[0004] Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.

[0005] The precursor of the cyclized resin such as a polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in a cured product.

[0006] The resin composition can be applied by a known coating method, etc., so it can be said that, for example, the applied resin composition has a high degree of freedom in designing the shape, size, and application position when applied, and has excellent adaptability in manufacturing. In addition to the high performance of cyclized resins such as polyimide, from the perspective of such excellent adaptability in manufacturing, the application development of the above-mentioned resin composition in the industry is increasingly expected.

[0007] For example, Patent Document 1 describes a resin composition comprising (A) a polyimide precursor, (B) a compound having a heterocyclic structure having a pka of 8.30 to 8.80 and containing a nitrogen atom, and (C) 5-amino-1H-tetrazole.

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2020-002281 Summary of the invention

[0011] Technical issues to be solved by the invention

[0012] In a component having a cured film containing a cyclized resin such as polyimide and a metal (e.g., a metal layer) in contact with the cured film (e.g., a device using the cured film as an insulating film), it is required that peeling between the metal and the cured film is not likely to occur even after a long period of time.

[0013] The object of the present invention is to provide a resin composition that can obtain a cured product that is not prone to peeling between metal and the cured product even after a long period of time, a cured product obtained by curing the above-mentioned resin composition, a laminate containing the above-mentioned cured product, a method for manufacturing the above-mentioned cured product, and a semiconductor device containing the above-mentioned cured product or the above-mentioned laminate.

[0014] Means for solving technical problems

[0015] Examples of representative embodiments of the present invention are shown below.

[0016] <1> A resin composition comprising:

[0017] Cyclized resin or its precursor; and

[0018] Nitrogen compounds,

[0019] The nitrogen-containing compound contains a nitrogen-containing heterocycle and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms as a ring member of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

[0020] <2> according to <1> The resin composition, wherein the nitrogen-containing heterocyclic ring comprises an imidazole skeleton, a triazole skeleton or a tetrazole skeleton.

[0021] <3> according to <1> or <2> The resin composition, wherein the amino group contained in the nitrogen-containing compound is unsubstituted.

[0022] <4> according to <1> to <3> The resin composition described in any one of the preceding claims, wherein a length of a connecting chain between a nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound and a nitrogen atom of the amino group is 3 or less.

[0023] <5> according to <1> to <4> The resin composition described in any one of the preceding claims, wherein a nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound is directly bonded to a carbonyl group.

[0024] <6> according to <1> to <5> The resin composition described in any one of the preceding claims, wherein the nitrogen-containing compound is a compound represented by any of the following formulas (1-1), (2-1) or (3-1);

[0025] [Chemical formula 1]

[0026]

[0027] In formula (1-1), R 1 represents a monovalent organic group, R 1a Each independently represents a hydrogen atom or a substituent, R N1 represents a hydrogen atom or a substituent;

[0028] In formula (2-1), R 2 represents a monovalent organic group, R 2a represents a hydrogen atom or a substituent, R N2 represents a hydrogen atom or a substituent;

[0029] In formula (3-1), R 3 represents a monovalent organic group, R N3 represents a hydrogen atom or a substituent.

[0030] <7> according to <1> to <6> The resin composition described above, wherein the molecular weight of the nitrogen-containing compound is less than 2,000.

[0031] <8> according to <1> to <7> The resin composition described in any one of the above is used for forming an interlayer insulating film for a redistribution layer.

[0032] <9> A solidified material, which is <1> to <8> The resin composition described in any one of the above is cured.

[0033] <10> A laminate comprising two or more layers of <9> The layers are formed of the above-mentioned cured product, and a metal layer is included between any layers of the layers formed of the above-mentioned cured product.

[0034] <11> A method for producing a solidified product, comprising: <1> to <8> Any of the resin compositions is preferably used in a film forming step of forming a film on a substrate.

[0035] <12> according to <11> The method for producing a cured product comprises an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

[0036] <13> according to <11> or <12> The method for producing the cured product comprises a heating step of heating the film at 50 to 450°C.

[0037] <14> A semiconductor device comprising <9> The solidified material or <10> The laminated body.

[0038] Effects of the Invention

[0039] According to the present invention, there are provided a resin composition capable of obtaining a cured product in which peeling between metal and the cured product is not likely to occur even after a long period of time, 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, and a semiconductor device containing the above cured product or the above laminate. DETAILED DESCRIPTION

[0040] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0041] In the present specification, a numerical range expressed by the symbol “to” indicates a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0042] In the present specification, the term "step" refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0043] Regarding the marking of groups (atomic groups) in this specification, the markings not marked as substituted and unsubstituted include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

[0044] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, electron beams, and other activating rays or radiation.

[0045] In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either “acryloyl” and “methacryloyl”.

[0046] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0047] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components excluding the solvent relative to the total mass of the composition.

[0048] In this specification, as long as there is no special description, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, about weight average molecular weight (Mw) and number average molecular weight (Mn), for example, can be obtained by using HLC-8220GPC (TOSOH CORPORATION system), and guard column HZ-L, TSK gel Super HZM-M, TSKgelSuper HZ4000, TSKgelSuperHZ3000 and TSKgel Super HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as column. As long as there is no special description, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, in the case where THP is not suitable as eluent, NMP (N- methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254 nm was used for detection in GPC measurement.

[0049] In this specification, about the positional relationship of each layer constituting the laminate, when it is recorded as "up" or "down", as long as there are other layers on the upper side or lower side of the layer that becomes the benchmark in the multiple layers concerned. That is, the third layer or element can also be further sandwiched between the layer that becomes the benchmark and the above-mentioned other layers, and the layer that becomes the benchmark does not need to contact the above-mentioned other layers. And, as long as there is no special explanation, the direction of the gradually stacked layer for the substrate is referred to as "up", or in the case of the presence of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and its opposite direction is referred to as "down". In addition, the setting of such up and down directions is for the convenience of explaining this specification, and in actual mode, the "up" direction in this specification can also be different from the vertical upward direction.

[0050] In this specification, unless otherwise specified, as each component contained in the composition, the composition may also contain two or more compounds corresponding to the component. Also, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component.

[0051] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0052] In the present specification, a combination of preferred embodiments is more preferred.

[0053] (Resin composition)

[0054] The resin composition of the present invention comprises a cyclized resin or a precursor thereof (hereinafter also referred to as a "specific resin") and a nitrogen-containing compound (hereinafter also referred to as a "specific nitrogen-containing compound"), wherein the specific nitrogen-containing compound comprises a nitrogen-containing heterocycle and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

[0055] The resin composition of the present invention is preferably used to form a photosensitive film to be exposed and developed, and is preferably used to form a film to be exposed and developed using a developer containing an organic solvent.

[0056] The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.

[0057] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive-tone development or a photosensitive film for negative-tone development.

[0058] In the present invention, negative-tone development refers to development in which non-exposed portions are removed by development during exposure and development, and positive-tone development refers to development in which exposed portions are removed by development.

[0059] As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product, and the developer and the development method described in the development step can be used.

[0060] According to the resin composition of the present invention, it is possible to obtain a cured product in which separation between the metal and the cured product is unlikely to occur even after a long period of time.

[0061] The mechanism by which the above-mentioned effects can be obtained is not yet clear, but is presumed to be as follows.

[0062] Conventionally, tetrazole or aminotetrazole has been used in cured films to improve adhesion to metals (for example, Patent Document 1). However, there is still room for improvement in terms of adhesion between metals and cured films over a long period of time.

[0063] Therefore, the present inventors have conducted intensive studies and found that a cured film having excellent adhesion between metal and the cured film after a long period of time can be obtained by using a nitrogen-containing compound (hereinafter also referred to as a "specific nitrogen-containing compound"), wherein the nitrogen-containing compound contains a nitrogen-containing heterocyclic ring and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and the nitrogen atom of the heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

[0064] The mechanism by which the above-mentioned effects can be obtained is not yet clear, but is presumed to be as follows.

[0065] The specific nitrogen-containing compound generates a carbonyl group, a sulfonyl group or a thiocarbonyl group by heating during the formation of a cured film, or decomposes at a position such as a carbonyl group to generate a compound that has high adsorption to metals and forms a hydrogen bond or a covalent bond with the polymer, thereby presumably improving the adhesion between the cured film and the metal.

[0066] If an example of a specific nitrogen-containing compound is given for explanation, it is presumed that the following specific nitrogen-containing compound is transferred as shown in the following formula (S1) or decomposed as shown in the formula (S2) by heating. Here, it is considered that the amide bond contained in the transferred compound in (S1) is hydrogen-bonded with the polymer and the nitrogen-containing heterocycle forms a complex with the metal, or the amino group contained in the decomposition product in (S2) forms a covalent bond with the polymer and the nitrogen-containing heterocycle forms a complex with the metal, etc., so that the adhesion between the cured film and the metal can be improved.

[0067] [Chemical formula 2]

[0068]

[0069] In addition, the specific nitrogen-containing compound before transfer or decomposition is easily dispersed in the composition film in a nearly uniform state, and the probability of being present near the metal in the cured film becomes high. Therefore, it is believed that the compound generated after the transfer or decomposition is also easily distributed near the metal, and as a result, it is easy to improve the adhesion between the cured film and the metal layer.

[0070] In addition, as described above, by heating during the formation of the cured film, a specific nitrogen-containing compound is transferred or decomposed to produce a compound that has high adsorption to metals and forms a hydrogen bond or a covalent bond with the polymer. Therefore, it is speculated that even after a long time, it is difficult for voids to be generated at the boundary between the cured film and the metal layer after curing.

[0071] Furthermore, it is considered that the basicity of the specific nitrogen-containing compound before migration or decomposition is low, and therefore the storage stability during storage of the composition is also excellent.

[0072] Here, Patent Document 1 does not describe a specific nitrogen-containing compound.

[0073] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0074] <Specific resin>

[0075] The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.

[0076] The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0077] In the present invention, the main chain means the relatively longest bonding chain in the resin molecule.

[0078] Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.

[0079] The precursor of the cyclized resin is a resin that changes its chemical structure due to external stimulation to become a cyclized resin, preferably a resin that changes its chemical structure due to heat, and more preferably a resin that forms a ring structure due to a ring-closing reaction due to heat to become a cyclized resin.

[0080] Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.

[0081] That is, the resin composition of the present invention preferably contains, as the specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamideimide, and a polyamideimide precursor.

[0082] The resin composition of the present invention preferably contains a polyimide or a polyimide precursor as a specific resin.

[0083] Furthermore, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0084] When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably includes a free radical polymerization initiator described below, more preferably includes a free radical polymerization initiator described below and includes a free radical crosslinking agent described below. In addition, as required, a sensitizer described below can be included. For example, a negative photosensitive film is formed by such a resin composition of the present invention.

[0085] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0086] 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 chemically amplified positive photosensitive film or a negative photosensitive film is formed from such a resin composition of the present invention.

[0087] 〔Polyimide precursor〕

[0088] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but the polyimide precursor preferably contains a repeating unit represented by the following formula (2).

[0089] [Chemical formula 3]

[0090]

[0091] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

[0092] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NH-, and is preferably an oxygen atom.

[0093] R in formula (2) 111 Represents a divalent organic group. As a divalent organic group, a group containing a straight-chain or branched aliphatic group, a cyclic aliphatic group and an aromatic group can be exemplified, preferably a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms or a group consisting of a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The above-mentioned straight-chain or branched aliphatic group may be substituted by a group containing a heteroatom by a hydrocarbon group in the chain, and the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom by a hydrocarbon group in the ring member. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. wherein Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

[0094] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0095] Specifically, diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof are preferred, and diamines containing an aromatic group having 6 to 20 carbon atoms are more preferred. The linear or branched aliphatic group may be substituted by a group containing a heteroatom in the hydrocarbon group in the chain, and the cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom in the hydrocarbon group of the ring member. Examples of the group containing an aromatic group include the following.

[0096] [Chemical formula 4]

[0097]

[0098] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO 2 -, -NHCO- or a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S- or -SO 2 - is more preferably -CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C(CH 3 ) 2 -.

[0099] In the formula, * indicates the bonding site with other structures.

[0100] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane 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'-diamino biphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy 4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone , 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2 -bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis( At least one diamine selected from the group consisting of 4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaterphenyl.

[0101] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0102] Furthermore, it is also preferable to use a diamine having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598.

[0103] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-, wherein Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 The aliphatic hydrocarbon group here is preferably an alkylene group.

[0104] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, preferred are divalent organic groups represented by formula (61).

[0105] Formula (51)

[0106] [Chemical formula 5]

[0107]

[0108] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0109] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0110] [Chemical formula 6]

[0111]

[0112] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

[0113] Examples of diamines that provide a structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0114] R in formula (2) 115The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).

[0115] In formula (5) or (6), * each independently represents a bonding site with another structure.

[0116] [Chemical formula 7]

[0117]

[0118] In formula (5), R 112 is a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - and -NHCO-, and a group in combination thereof is more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO 2 - is further preferably selected from -CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 - is a divalent group.

[0119] About R 115 Specifically, the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride can be cited. 115 In the corresponding structure, the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types.

[0120] It is preferable that tetracarboxylic dianhydride is represented by the following formula (O).

[0121] [Chemical formula 8]

[0122]

[0123] In formula (O), R 115 represents a tetravalent organic group. 115 With R in formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0124] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-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'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, and 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 alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms thereof.

[0125] Furthermore, preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0126] In formula (2), R 111 and R 115 At least one of R may also have an OH group. More specifically, 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0127] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114At least one of them contains more than two polymerizable groups. As a polymerizable group, it is a group that can be cross-linked by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As the free radical polymerizable group possessed by the polyimide precursor, it is preferably a group with an ethylenically unsaturated bond.

[0128] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). Preferably, the group is represented by the following formula (III).

[0129] [Chemical formula 9]

[0130]

[0131] In formula (I[I), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0132] In formula (III), * represents a bonding site with other structures.

[0133] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH a CH(OH)CH 2 -, cycloalkylene or polyalkyleneoxy.

[0134] Preferred R 201 Examples of alkylene groups include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy, more preferably alkylene such as ethylene and propylene, -CH 2 CH(OH)CH 2 -, cyclohexyl, or polyalkyleneoxy, and more preferably, an alkylene or polyalkyleneoxy group such as ethylene or propylene.

[0135] In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0136] When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0137] The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0138] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0139] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0140] As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group obtained by bonding a plurality of ethyleneoxy groups to a plurality of propyleneoxy groups, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and further preferably a polyethyleneoxy group. In the group obtained by bonding a plurality of ethyleneoxy groups to a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternation. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0141] In formula (2), R 113 In the case of a hydrogen atom or in R 114 When it is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0142] In formula (2), R 113 and R 114 At least one of the groups may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is a group that decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc., and is more preferably an acetal group or a ketal group from the viewpoint of exposure sensitivity.

[0143] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0144] Furthermore, the polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0145] Furthermore, in order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0146] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain a repeating unit represented by formula (2-A), the width of the exposure latitude can be further expanded.

[0147] Formula (2-A)

[0148] [Chemical formula 10]

[0149]

[0150] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0151] A 1 , A 2 , R 111 , R 113 and R 114 and A in formula (2) independently. 1 , A 2 , R 111 , R 113 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0152] R 112 With R in formula (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0153] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating units represented by formula (2). Furthermore, in addition to the repeating units of the above formula (2), the polyimide precursor may also contain other types of repeating units.

[0154] As one embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by formula (2) can be cited as 50 mol% or more of all repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide precursor except the terminal can also be repeating units represented by formula (2).

[0155] 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. 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.

[0156] The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0157] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0158] Furthermore, when the resin composition includes a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the plurality of polyimide precursors as one resin are within the above ranges, respectively.

[0159] 〔Polyimide〕

[0160] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0161] In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more of 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C., preferably dissolves 0.5 g or more of the polyimide from the viewpoint of pattern formation, and more preferably dissolves 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0162] Furthermore, from the viewpoint of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0163] In the present specification, the “main chain” refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and the “side chain” refers to other bond chains.

[0164] -Fluorine atom-

[0165] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms.

[0166] The fluorine atom is preferably present in R 132 or R in the repeating unit represented by the formula (4) described below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a fluorinated alkyl group is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0167] The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less relative to the total mass of the polyimide.

[0168] -Silicon Atoms-

[0169] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.

[0170] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 Among them, R in the repeating unit represented by the formula (4) described below is more preferably included as an organo-modified (poly)siloxane structure described below. 131 middle.

[0171] Furthermore, the silicon atom or the organo-modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

[0172] The amount of silicon atoms is preferably 1% by mass or more, and more preferably 20% by mass or less, based on the total mass of the polyimide.

[0173] -Ethylenically unsaturated bond-

[0174] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0175] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0176] The ethylenically unsaturated bond preferably has radical polymerizability.

[0177] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0178] Among these, the ethylenically unsaturated bond is preferably contained in R 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond is more preferably 131 middle.

[0179] Examples of the group having an ethylenically unsaturated bond include groups directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group and having a vinyl group which may be substituted, a (meth)acryloyl group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0180] [Chemical formula 11]

[0181]

[0182] In formula (IV), R 20 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0183] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3) or a group obtained by combining two or more of these.

[0184] Furthermore, the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof.

[0185] 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.

[0186] Among these, R 21 The group is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0187] [Chemical formula 12]

[0188]

[0189] 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 obtained by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bond with R in formula (IV). 21 The bonding site of the bonded oxygen atom.

[0190] In the formulae (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as the above R 21 The preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same.

[0191] In formula (R1), X is preferably an oxygen atom.

[0192] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same.

[0193] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanateethyl methacrylate).

[0194] The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0195] The structure represented by the formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0196] In formula (IV), * represents a bonding site to other structures, and is preferably a bonding site to the main chain of the polyimide.

[0197] The amount of the ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g, based on the total mass of the polyimide.

[0198] -Polymerizable groups other than groups having ethylenically unsaturated bonds-

[0199] The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.

[0200] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0201] The polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in R 131 middle.

[0202] The amount of the polymerizable groups other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, based on the total mass of the polyimide.

[0203] -Polarity conversion group-

[0204] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same and the preferred embodiments are also the same.

[0205] The polarity conversion group is, for example, R 131 , R 132 , the end of polyimide, etc.

[0206] -Acid value-

[0207] When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0208] Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0209] When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described below), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and further preferably 5 to 20 mgKOH / g.

[0210] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0211] Furthermore, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred.

[0212] pKa refers to a value expressed by its negative common logarithm pKa of the equilibrium constant Ka in consideration of the dissociation reaction of releasing hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is a calculated value based on ACD / ChemSketch (registered trademark). Alternatively, reference may be made to the values ​​disclosed in the "Revised 5th Edition of the Handbook of Chemistry, Basic Edition" compiled by the Chemical Society of Japan.

[0213] Furthermore, when the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0214] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0215] -Phenolic hydroxyl group-

[0216] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0217] The polyimide may have a phenolic hydroxyl group at a main chain terminal or in a side chain.

[0218] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0219] 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 polyimide.

[0220] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[0221] [Chemical formula 13]

[0222]

[0223] In formula (4), R 131 represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0224] In the case of having a polymerizable group, the polymerizable group may be located at R 131 and R 132 At least one of them may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0225] Formula (4-1)

[0226] [Chemical formula 14]

[0227]

[0228] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0229] Formula (4-2)

[0230] [Chemical formula 15]

[0231]

[0232] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

[0233] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond.

[0234] R 131 The divalent organic group includes the following: 111 The same groups have the same preferred range.

[0235] And, as R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 Example.

[0236] From the perspective of more effectively suppressing the warping during calcination, R 131The diamine residue having at least two alkylene glycol units in the main chain is preferred. The diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule is more preferred. The diamine residue containing no aromatic ring is further preferred.

[0237] Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by HUNTSMAN CORPORATION), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

[0238] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include 115 The same groups have the same preferred range.

[0239] For example, as R 115 The four bonders of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

[0240] And, R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0241] R is also preferred 131 and R 132 More specifically, at least one of R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) can be mentioned as preferred examples, and R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be cited.

[0242] Furthermore, the polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more and preferably 20% by mass or less.

[0243] Furthermore, in order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like can be cited.

[0244] In addition, in order to improve the storage stability of the resin composition, it is preferred to seal the main chain end of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, or a monoactive ester compound. Among these, monoamines are more preferably used, and preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different terminal groups can be introduced.

[0245] -Imidization rate (ring closure rate)-

[0246] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0247] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0248] The imidization ratio is measured, for example, by the following method.

[0249] The infrared absorption spectrum of polyimide was measured and the absorption peak at 1377 cm-1 derived from the imide structure was determined. -1Next, the polyimide was heat treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again to obtain the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0250] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0251] Polyimides may all contain one R 131 or R 132 The repeating unit represented by the above formula (4) may also contain two or more different types of R 131 or R 132 The polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, the repeating units represented by the above formula (2).

[0252] Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with diamine (a capping agent partially substituted with monoamine) at low temperature; a method of reacting tetracarboxylic dianhydride (a capping agent partially substituted with acid anhydride, monochloride compound or monoactive ester compound) with diamine at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting the diester with diamine (a capping agent partially substituted with monoamine) in the presence of a condensing agent; a method of obtaining a polyimide precursor by a method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then chlorinating the remaining dicarboxylic acid and reacting the diester with diamine (a capping agent partially substituted with monoamine), and completely imidizing the diester using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer and the polyimide precursor. Furthermore, other known methods for synthesizing polyimide can also be applied.

[0253] 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 folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

[0254] Furthermore, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0255] The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0256] Furthermore, when the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the multiple polyimides as one resin are within the above ranges, respectively.

[0257] 〔Polybenzoxazole precursor〕

[0258] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferred that the polybenzoxazole precursor contains a repeating unit represented by the following formula (3).

[0259] [Chemical formula 16]

[0260]

[0261] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0262] In formula (3), R 123 and R 124 Respectively with R in formula (2) 113 The meanings of are the same, and the preferred ranges are also the same. That is, it is preferred that at least one of them is a polymerizable group.

[0263] In formula (3), R 121 represents a divalent organic group. As the divalent organic group, it is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, it is preferably a straight-chain aliphatic group. R 121 A dicarboxylic acid residue is preferred. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0264] As the dicarboxylic acid residue, a dicarboxylic acid residue 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.

[0265] As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.

[0266] Examples of the dicarboxylic acid containing a linear aliphatic group 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-tetrafluorohexane. Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and dicarboxylic acids represented by the following formula, etc.

[0267] [Chemical formula 17]

[0268]

[0269] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0270] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids containing only a group having an aromatic group and two -COOH groups are more preferred.

[0271] [Chemical formula 18]

[0272]

[0273] In the formula, A represents a 2 -、-O-、-S-、-SO 2-、-CO-、-NHCO-、-C(CF 3 ) 2 - and -C(CH 3 ) 2 -, and * each independently represents a bonding site to other structures.

[0274] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4′-carbonyldibenzoic acid, 4,4′-dicarboxydiphenyl ether, and phthalic acid.

[0275] In formula (3), R 122 represents a tetravalent organic group. As a tetravalent organic group, R 115 The meanings are the same, and the preferred ranges are also the same.

[0276] And, R 122 The group derived from a bisaminophenol derivative is preferred. Examples of the group derived from a bisaminophenol derivative include 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- 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. These bis-aminophenols can be used alone or in combination.

[0277] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0278] [Chemical formula 19]

[0279]

[0280] Where, X 1 Indicates -O-, -S-, -C(CF 3 ) 2 -、-CH 2 -、-SO 2-, -NHCO-, * and # represent the bonding sites with other structures respectively. 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. 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferred that any two of them are the same as R in formula (3). 122 The bonding site of the nitrogen atom to which the bond is attached and the other two are R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached is preferably 2 * to R in formula (3). 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded, or the two * are R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded and the two # are the same as R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached is preferably 2 * which is the same as R in formula (3). 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the bonded nitrogen atom.

[0281] The bisaminophenol derivative is also preferably a compound represented by formula (As).

[0282] [Chemical formula 20]

[0283]

[0284] In formula (As), R 1 is selected from the group consisting of a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond or an organic group in the group of the following formula (A-sc). 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. 3 It is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[0285] [Chemical formula 21]

[0286]

[0287] (In formula (A-sc), * represents a bond to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

[0288] In the above formula (As), it is considered that the ortho position of the phenolic hydroxyl group, that is, R 3 Having a substituent also on the amide bond is particularly preferred in that the carbonyl carbon of the amide bond and the hydroxyl group are brought closer together, thereby further increasing the effect of achieving a high cyclization rate during curing at a low temperature.

[0289] Furthermore, in the above formula (As), R 2 is an alkyl group and R 3 An alkyl group is preferred because it can maintain high transparency to i-rays and achieve a high cyclization rate when cured at a low temperature.

[0290] Furthermore, in the above formula (As), R 1 More preferably, R is an alkylene group or a substituted alkylene group. 1 Specific examples of the alkylene group and the substituted alkylene group include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH is more preferred in terms of obtaining a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining high transparency to i-rays and a high cyclization rate when cured at a low temperature. 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -.

[0291] As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506 can be referred to, and these contents are incorporated into the present specification.

[0292] Specific examples of the structure of the bisaminophenol derivative represented by the formula (As) include the structures described in paragraphs 0070 to 0080 of JP-A-2013-256506, and these contents are incorporated into the present specification. Of course, it is not limited to these.

[0293] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of the above formula (3).

[0294] The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in order to suppress the occurrence of warpage associated with ring closure.

[0295] [Chemical formula 22]

[0296]

[0297] In formula (SL), Z has structure a and structure b, and R1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the mole % of the Z part, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a+b is 100 mole %.

[0298] In formula (SL), preferred Z includes R in structure b. 5s and R 6s The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and the effect of suppressing warping and the effect of improving solvent solubility can be achieved.

[0299] When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R in the formula (2): 115 Example.

[0300] The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000, and the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200.

[0301] The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly specified, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[0302] Furthermore, when the resin composition contains a plurality of polybenzoxazole precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersity of at least one polybenzoxazole precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersity calculated using the plurality of polybenzoxazole precursors as one resin are within the above ranges.

[0303] 〔Polybenzoxazole〕

[0304] As polybenzoxazole, as long as it is a polymer compound having a benzoxazole ring, it is not particularly limited, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it can also be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group.

[0305] [Chemical formula 23]

[0306]

[0307] In formula (X), R 133 represents a divalent organic group, R 134 It represents a tetravalent organic group.

[0308] In the case of having a polarity conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134 At least one of them may be located at a terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0309] Formula (X-1)

[0310] [Chemical formula 24]

[0311]

[0312] In formula (X-1), R 135 and R 136 At least one of them is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X).

[0313] Formula (X-2)

[0314] [Chemical formula 25]

[0315]

[0316] In formula (X-2), R137 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The other groups have the same meanings as in formula (X).

[0317] The polarity conversion group such as the polymerizable group or the acid-decomposable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor.

[0318] R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. As a specific example, R in the formula (3) of the polybenzoxazole precursor may be 121 And, its preferred example is the same as R 121 same.

[0319] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor: 122 And, its preferred example is the same as R 122 same.

[0320] For example, as R 122 The four bonders 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. 134 In the case of the following organic groups, the following structures are formed. In the following structures, * represents a bonding site to a nitrogen atom or an oxygen atom in formula (X).

[0321] [Chemical formula 26]

[0322]

[0323] The oxazolidinylation rate of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolidinylation rate is 85% or more, the film shrinkage caused by the ring closure generated during the oxazolidinylation by heating is reduced, thereby being able to more effectively suppress the occurrence of warping.

[0324] The oxazolylation rate is measured, for example, by the following method.

[0325] The infrared absorption spectrum of polybenzoxazole was measured and the absorption peak at 1650 cm-1, which is derived from the amide structure of the precursor, was determined. -1 Next, at 1490 cm -1 The polybenzoxazole was heat treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again to determine the absorption intensity of the aromatic ring at 1650cm -1The peak intensity Q2 is near 1490 cm -1 The absorption intensity of the aromatic ring found nearby is normalized. Using the obtained standard values ​​of the peak intensities Q1 and Q2, the oxazolylation rate of the polybenzoxazole can be calculated according to the following formula.

[0326] Oxazolidinylation rate (%) = (standard value of peak intensity Q1 / standard value of peak intensity Q2) × 100

[0327] Polybenzoxazoles may all contain one R 131 or R 132 The repeating unit of the above formula (X) may also contain two or more different types of R 131 or R 132 In addition to the repeating unit of the above formula (X), the polybenzoxazole may contain other types of repeating units.

[0328] Regarding polybenzoxazole, for example, by reacting a bisaminophenol derivative with a poly(vinyl alcohol) containing R 133 The polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives of the dicarboxylic acid to obtain the polybenzoxazole precursor, and then oxazolating the precursor by a known oxazolylation reaction method.

[0329] In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to improve the reaction yield.

[0330] 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 folding 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. In addition, in the case of containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[0331] Furthermore, the number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0332] The molecular weight dispersion of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole is not particularly specified, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[0333] Furthermore, when the resin composition contains a plurality of polybenzoxazoles as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersity of at least one polybenzoxazole are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersity calculated using the plurality of polybenzoxazoles as one resin are within the above ranges.

[0334] 〔Polyamide-imide precursor〕

[0335] The polyamideimide precursor preferably includes a repeating unit represented by the following formula (PAI-2).

[0336] [Chemical formula 27]

[0337]

[0338] In the formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 It represents a hydrogen atom or a monovalent organic group.

[0339] In the formula (PAI-2), R 117 Examples include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups 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 obtained by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0340] The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)- 2 -, alkylene, halogenated alkylene, arylene or a linking group formed by bonding two or more of these, more preferably -O-, -S-, alkylene, halogenated alkylene, arylene or a linking group formed by bonding two or more of these.

[0341] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0342] As the above-mentioned 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. Furthermore, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by a halogen atom, but preferably all hydrogen atoms are substituted by a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0343] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0344] And, R 117 It is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. The halogenation is preferably chlorination.

[0345] In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0346] Two of the three carboxyl groups of the tricarboxylic acid compound may be converted to anhydride.

[0347] Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.

[0348] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0349] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing 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 obtained by combining two or more of these groups via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0350] Specific examples of the tricarboxylic acid compound include: 2 -、-C(CH 3 ) 2-、-C(CF 3 ) 2 -、-SO 2 - or phenylene-linked 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, a compound of phthalic acid (or phthalic anhydride) and benzoic acid.

[0351] These compounds may be compounds in which two carboxyl groups are anhydrified (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

[0352] In the formula (PAI-2), R 111 , A 2 , R 113 Respectively with R in the above formula (2) 111 , A 2 , R 113 The meanings are the same and the preferred aspects are also the same.

[0353] The polyamideimide precursor may further include other repeating units.

[0354] Examples of other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0355] [Chemical formula 28]

[0356]

[0357] In the formula (PAI-1), R 116 represents a divalent organic group, R 111 It represents a divalent organic group.

[0358] In the formula (PAI-1), R 116 Examples include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups 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 obtained by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0359] The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)- 2-, alkylene, halogenated alkylene, arylene or a linking group formed by bonding two or more of these, more preferably -O-, -S-, alkylene, halogenated alkylene, arylene or a linking group formed by bonding two or more of these.

[0360] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0361] As the above-mentioned 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. Furthermore, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by a halogen atom, but preferably all hydrogen atoms are substituted by a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0362] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0363] And, R 116 It is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

[0364] In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.

[0365] 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.

[0366] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated and is used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.

[0367] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0368] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing 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 obtained by combining two or more of these groups via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0369] 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, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, 2,6-tetrafluorohexadecanoic acid, 1,2-dimethyl ... Sebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0370] Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups in the above-mentioned specific examples of the dicarboxylic acid compound are halogenated.

[0371] In the formula (PAI-1), R 111 With R in the above formula (2) 111 The meanings are the same and the preferred aspects are also the same.

[0372] Furthermore, the polyamide-imide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0373] Furthermore, in order to improve the adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0374] As one embodiment of the polyamide-imide precursor in the present invention, the total content of the repeating unit represented by the formula (PA1-2), the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal can be any one of the repeating units represented by the formula (PAI-2), the repeating units represented by the formula (PAI-1) and the repeating units represented by the formula (2).

[0375] In addition, as another embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more of all repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamide-imide precursor except the terminal can be any one of the repeating units represented by the formula (PAI-2) or the repeating units represented by the formula (PAI-1).

[0376] 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. 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.

[0377] The molecular weight dispersion of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyamideimide precursor is not particularly specified, for example, preferably 7.0 or less, more preferably 6.5 or less, and more preferably 6.0 or less. In addition, when the resin composition includes a plurality of polyamideimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyamideimide precursor are within the above range. In addition, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the plurality of polyamideimide precursors as one resin are within the above range.

[0378] 〔Polyamide-imide〕

[0379] 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.

[0380] In this specification, the alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves 0.1 g or more of 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C., and preferably dissolves 0.5 g or more of the polyamide-imide from the viewpoint of pattern formation, and more preferably dissolves 1.0 g or more of the polyamide-imide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0381] Furthermore, from the viewpoint of film strength and insulation properties 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.

[0382] -Fluorine atom-

[0383] From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has a fluorine atom.

[0384] The fluorine atom is preferably present in R 117 or R 111 Among them, R contained as a fluorinated alkyl group in the repeating unit represented by the formula (PAI-3) described later is more preferably 117 or R 111 middle.

[0385] The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less relative to the total mass of the polyamideimide.

[0386] -Ethylenically unsaturated bond-

[0387] From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

[0388] The polyamideimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0389] The ethylenically unsaturated bond preferably has radical polymerizability.

[0390] The ethylenically unsaturated bond preferably includes R 117 or R 111 Among them, R contained in the repeating unit represented by the formula (PAI-3) described later as a group having an ethylenically unsaturated bond is more preferably 117 or R 111 middle.

[0391] Preferred embodiments of the group having an ethylenically unsaturated bond are the same as preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0392] The amount of the ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, based on the total mass of the polyamide-imide.

[0393] -Polymerizable groups other than ethylenically unsaturated bonds-

[0394] The polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.

[0395] Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide.

[0396] The polymerizable group other than the ethylenically unsaturated bond is preferably contained in R 111 middle.

[0397] The amount of the polymerizable groups other than the ethylenically unsaturated bonds is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g, based on the total mass of the polyamideimide.

[0398] -Polarity conversion group-

[0399] The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same and the preferred embodiments are also the same.

[0400] -Acid value-

[0401] When the polyamideimide is subjected to alkaline development, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0402] Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0403] When the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described below), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and further preferably 5 to 20 mgKOH / g.

[0404] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0405] Furthermore, examples of the acid group contained in the polyamide-imide include the same groups as the acid groups in the above-mentioned polyimide, and preferred aspects are also the same.

[0406] -Phenolic hydroxyl group-

[0407] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

[0408] The polyamideimide may have a phenolic hydroxyl group at a main chain terminal or in a side chain.

[0409] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (PAI-3) described below. 117 or R 111 middle.

[0410] 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 polyamide-imide.

[0411] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[0412] [Chemical formula 29]

[0413]

[0414] In the formula (PAI-3), R 111 and R 117 Respectively with R in formula (PAI-2) 111 and R 117 The meanings are the same and the preferred aspects are also the same.

[0415] In the case of having a polymerizable group, the polymerizable group may be located at R 111 and R 117 At least one of the above may be located at the terminal of the polyamide-imide.

[0416] In order to improve the storage stability of the resin composition, the main chain ends of the polyamide-imide are preferably sealed with an end-capping agent such as a monoamine, anhydride, monocarboxylic acid, monochloride compound, or monoactive ester compound. The preferred embodiment of the end-capping agent is the same as the preferred embodiment of the end-capping agent in the above-mentioned polyimide.

[0417] -Imidization rate (ring closure rate)-

[0418] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0419] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0420] The imidization ratio is measured by the same method as the ring closure ratio of the polyimide.

[0421] The polyamide-imide may contain all of one R 111 or R 117 The repeating unit represented by the above formula (PAI-3) may also contain two or more different types of R 131 or R 132 The polyamide-imide may further comprise other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0422] Polyamideimide can be synthesized, for example, by the following methods: a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer and the polyamideimide precursor.

[0423] The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding 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.

[0424] Furthermore, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0425] The molecular weight dispersion of polyamideimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of polyamideimide is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0426] Furthermore, when the resin composition contains a plurality of polyamide-imides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyamide-imide are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the plurality of polyamide-imides as one resin are within the above ranges, respectively.

[0427] [Method for producing polyimide precursor, etc.]

[0428] The polyimide precursor can be obtained, for example, by the following methods: a method of reacting tetracarboxylic dianhydride and diamine at low temperature, a method of reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid and esterifying it using a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting them in the presence of diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with diamine, etc. Among the above-mentioned production methods, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with diamine is more preferred.

[0429] Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0430] Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.

[0431] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.

[0432] In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0433] The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0434] In the method for producing a polyimide precursor or the like, it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0435] The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0436] -Capping agent-

[0437] In the manufacturing method of polyimide precursor etc., in order to further improve storage stability, it is preferred to seal the carboxylic anhydride, anhydride derivative or amino group remaining in the resin terminal such as polyimide precursor. When sealing the carboxylic anhydride and anhydride derivative remaining in the resin terminal, as an end-capping agent, monohydric alcohol, phenol, mercaptan, thiophenol, monoamine etc. can be cited. From the viewpoint of reactivity and film stability, monohydric alcohol, phenols or monoamine are more preferably used. As the preferred compound of monohydric alcohol, methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, primary alcohols such as furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohols such as ... Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene. , 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different terminal groups can be introduced.

[0438] In addition, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group that can react with the amino group. The preferred sealant for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic anhydride, sulfonic acid carboxylic anhydride, etc., more preferably carboxylic anhydride, carboxylic acid chloride. As the preferred compound of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be cited. In addition, as the preferred compound of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, etc. can be cited.

[0439] -Solid Precipitation-

[0440] In the manufacturing method of polyimide precursor etc., the process of solid precipitation can be included. Specifically, after filtering out the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as required, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or its mixed solution, so that the polymer component is precipitated as a solid and dried, thereby obtaining polyimide precursor etc. In order to improve the degree of purification, the operation of redissolving, reprecipitating, drying etc. of polyimide precursor etc. can be repeated. In addition, the process of removing ionic impurities using ion exchange resin can be included.

[0441] 〔content〕

[0442] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the resin composition.

[0443] The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0444] Furthermore, the resin composition of the present invention also preferably contains at least two types of resins.

[0445] Specifically, the resin composition of the present invention may contain two or more specific resins and other resins described below in total, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0446] When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains a structure (R in the above formula (2)) derived from a dianhydride and which is a polyimide precursor. 115 ) Two or more different polyimide precursors.

[0447] <Other resins>

[0448] The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0449] Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0450] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[0451] For example, instead of or in addition to the polymerizable compound described below, a polymerizable group having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, a polymerizable group content of 1×10 -3 By adding the (meth)acrylic resin in an amount of 10 mol / g or more to the resin composition, the coating properties of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.

[0452] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0453] Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0454] Furthermore, as a preferred embodiment of the resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins is preferably 20% by mass or less relative to the total solid content of the resin composition, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0455] The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more other resins, the total amount is preferably within the above range.

[0456] <Specific nitrogen-containing compounds>

[0457] The resin composition of the present invention contains a nitrogen-containing compound, wherein the nitrogen-containing compound contains a nitrogen-containing heterocycle and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

[0458] 〔Nitrogen-containing heterocyclic ring〕

[0459] The nitrogen-containing heterocycle in the specific nitrogen-containing compound is a heterocycle containing a nitrogen atom as a ring member.

[0460] The nitrogen-containing heterocyclic ring may be a monocyclic ring or a bicyclic ring, and is preferably a monocyclic ring or a condensed ring, more preferably a 5-membered or 6-membered monocyclic ring, a condensed ring of 5-membered rings, a condensed ring of 6-membered rings, or a condensed ring of a 5-membered ring and a 6-membered ring, and more preferably a 5-membered monocyclic ring or a condensed ring of a 5-membered ring and a 6-membered ring.

[0461] The number of nitrogen atoms contained in the nitrogen-containing heterocyclic ring is preferably 1 to 4, more preferably 2 to 4.

[0462] The nitrogen-containing heterocyclic ring may contain heteroatoms other than nitrogen atoms as ring members, but an embodiment in which the nitrogen-containing heterocyclic ring does not contain heteroatoms other than nitrogen atoms as ring members is also a preferred embodiment of the present invention. Examples of the heteroatoms other than nitrogen atoms include oxygen atoms, sulfur atoms, and the like.

[0463] The nitrogen-containing heterocyclic ring may be an aliphatic ring or an aromatic ring, but is preferably an aromatic ring.

[0464] The specific nitrogen-containing compound may have two or more nitrogen-containing heterocyclic rings in its structure, but an embodiment in which the specific nitrogen-containing compound has only one nitrogen-containing heterocyclic ring is also one of the preferred embodiments of the present invention.

[0465] When the specific nitrogen-containing compound has two or more nitrogen-containing heterocyclic rings, at least one of the nitrogen atoms serving as a ring member of at least one nitrogen-containing heterocyclic ring may be directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

[0466] From the perspective of adhesion after a long period of time, among these, the nitrogen-containing heterocyclic ring preferably contains an imidazole skeleton, a triazole skeleton or a tetrazole skeleton, more preferably an imidazole ring, a triazole ring, a tetrazole ring or a condensed ring of these rings with other rings, further preferably a benzimidazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring or an adenine ring.

[0467] The other ring is preferably an aromatic ring, more preferably a 5-membered or 6-membered aromatic ring, and more preferably a benzene ring.

[0468] 〔Amino〕

[0469] Certain nitrogen-containing compounds contain an amino group.

[0470] One of the hydrogen atoms of the amino group may be substituted, but is preferably unsubstituted from the viewpoint of adhesion over a long period of time.

[0471] The substituent when one of the amino groups is substituted is not particularly limited, and a known substituent can be used, but examples thereof include a hydrocarbon group or a hydrocarbon group containing one or more selected from -O-, -C(=O)-, -S- and -S(=O)- 2 -a group of at least one structure, etc.

[0472] The specific nitrogen-containing compound may have two or more amino groups, but an embodiment having only one amino group is also one of the preferred embodiments of the present invention.

[0473] The amino group may be directly bonded to the nitrogen-containing heterocyclic ring or may be bonded via a connecting chain.

[0474] As the connecting chain, a hydrocarbon group can be mentioned.

[0475] Here, an embodiment in which the amino group and the nitrogen-containing heterocyclic ring are directly bonded is also one of the preferred embodiments of the present invention.

[0476] The length of the connecting chain between the nitrogen atom of the nitrogen-containing heterocyclic ring member and the nitrogen atom of the amino group in the nitrogen-containing compound is preferably 3 or less, more preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0477] In this specification, "connection chain" refers to a chain connecting two atoms of the connection object or a connection atom group in the shortest (minimum number of atoms) way. For example, in the compound represented by the following formula, since there is 1 carbon atom on the shortest path, the length of the connection chain between the amino group and the nitrogen atom contained in the triazole ring as a nitrogen-containing heterocycle is 1.

[0478] [Chemical formula 30]

[0479]

[0480] 〔Carbonyl, sulfonyl or thiocarbonyl〕

[0481] In the specific nitrogen-containing compound, at least one of the nitrogen atoms serving as ring members of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

[0482] Among these, in the specific nitrogen-containing compound, at least one of the nitrogen atoms serving as ring members of the nitrogen-containing heterocyclic ring is preferably directly bonded to a carbonyl group or a sulfonyl group, and more preferably directly bonded to a carbonyl group.

[0483] Among these, the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the specific nitrogen-containing compound is preferably directly bonded to the carbonyl group from the viewpoint of adhesion after a long period of time.

[0484] The specific nitrogen-containing compound may have two or more carbonyl groups, sulfonyl groups or thiocarbonyl groups directly bonded to the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring, but an embodiment in which the specific nitrogen-containing compound has only one carbonyl group, sulfonyl group or thiocarbonyl group directly bonded to the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring is also one of the preferred embodiments of the present invention.

[0485] When the specific nitrogen-containing compound has two or more carbonyl groups, sulfonyl groups or thiocarbonyl groups directly bonded to the nitrogen atom which is a ring member of the nitrogen-containing heterocyclic ring, it may have two or more groups selected from the group consisting of only one of the carbonyl groups, sulfonyl groups and thiocarbonyl groups, or may have two or more groups selected from the group consisting of the carbonyl groups, sulfonyl groups and thiocarbonyl groups.

[0486] The group bonded to the side opposite to the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring in the carbonyl group, the sulfonyl group or the thiocarbonyl group in the specific nitrogen-containing compound is not particularly limited, but examples thereof include a hydrocarbon group or a hydrocarbon group and a group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O)- 2 - and -NR N -A group represented by a combination of at least one structure is preferably a hydrocarbon group.

[0487] Examples of the hydrocarbon group include alkyl groups, alkenyl groups, and aryl groups, preferably alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, or aromatic hydrocarbon groups having 6 to 20 carbon atoms, and more preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or aromatic hydrocarbon groups having 6 to 10 carbon atoms. These hydrocarbon groups may further have a substituent.

[0488] Specific examples include straight-chain alkyl groups such as methyl, ethyl and propyl groups, branched-chain alkyl groups such as isopropyl, tert-butyl and 2-ethylhexyl groups, cyclic alkyl groups such as cyclopentanyl, norbornyl, isobornyl and adamantyl groups, alkenyl groups such as methylvinyl groups, and aromatic hydrocarbon groups such as phenyl, naphthyl, 4-methylphenyl and 2,6-methylphenyl groups.

[0489] The above R N It represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0490] as a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O) 2 - and -NR N - is preferably a group represented by a combination of at least one structure selected from -O- and -NR N-, more preferably a group represented by the following formula (R-1) or (R-2).

[0491] [Chemical formula 31]

[0492]

[0493] In formula (R-1), R r1 represents a monovalent hydrocarbon group, R N As described above, * represents a bonding site to the above-mentioned carbonyl group, the above-mentioned sulfonyl group or the above-mentioned thiocarbonyl group.

[0494] In formula (R-2), R r2 represents a monovalent hydrocarbon group, L r1 and L r2 Each independently represents a divalent hydrocarbon group, and * represents a bonding site to the above-mentioned carbonyl group, the above-mentioned sulfonyl group or the above-mentioned thiocarbonyl group.

[0495] In formula (R-1), R r1 It is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0496] In formula (R-2), R r2 It is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0497] In formula (R-2), L r1 and L r2 Each of them independently is preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, further preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an ethylene group or a propylene group.

[0498] [Formula (1-1) to Formula (3-1)]

[0499] Among these, the specific nitrogen-containing compound is preferably a compound represented by any of the following formula (1-1), formula (2-1) or formula (3-1).

[0500] [Chemical formula 32]

[0501]

[0502] In formula (1-1), R 1 represents a monovalent organic group, R 1a Each independently represents a hydrogen atom or a substituent, R N1 represents a hydrogen atom or a substituent;

[0503] In formula (2-1), R 2 represents a monovalent organic group, R 2a represents a hydrogen atom or a substituent, R N2 represents a hydrogen atom or a substituent;

[0504] In formula (3-1), R 3 represents a monovalent organic group, R N3 represents a hydrogen atom or a substituent.

[0505] In formula (1-1), R 1 Preferred embodiments are the same as the preferred embodiments described above as the group bonded to the side opposite to the nitrogen atom which is a ring member of the nitrogen-containing heterocyclic ring among the carbonyl group, the sulfonyl group or the thiocarbonyl group.

[0506] In formula (1-1), R 1a Each independently represents a hydrogen atom or a substituent. 1a The substituent in includes hydrocarbon groups, halogen atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, etc., preferably hydrocarbon groups, more preferably alkyl groups having 1 to 10 carbon atoms. Among these, all R 1a For hydrogen atoms or R 1a One or two of them are substituents.

[0507] In formula (1-1), R N1 represents a hydrogen atom or a substituent, and is preferably a hydrogen atom. N1 Preferred embodiments when it is a substituent are the same as those explained above as the substituent in the amino group.

[0508] In formula (1-2), R 2 , R 2a and R N2 Respectively with R in formula (1-1) 1 , R 1a and R N1 The meanings are the same and the preferred aspects are also the same.

[0509] In formula (1-3), R 3 and R N3 Respectively with R in formula (1-1) 1 and R N1 The meanings are the same and the preferred aspects are also the same.

[0510] 〔Molecular weight〕

[0511] The molecular weight of the specific nitrogen-containing compound is preferably less than 2,000 from the viewpoint of adhesion after a long period of time.

[0512] The lower limit of the molecular weight is preferably 120 or more, more preferably 150 or more.

[0513] The upper limit of the molecular weight is more preferably less than 1,500, and further preferably less than 1,000.

[0514] Specific examples of the specific nitrogen-containing compound include the following compounds.

[0515] [Chemical formula 33]

[0516]

[0517] (Synthesis Method)

[0518] The synthesis method of the specific nitrogen-containing compound is not particularly limited, but for example, it can be obtained by reacting a nitrogen-containing heterocyclic compound having an amino group (one of the hydrogen atoms of the amino group may be substituted) with a carboxylic acid halide, a sulfonic acid halide, a thiocarboxylic acid halide, an isocyanate compound or a thioisocyanate compound. In addition, it can also be obtained by a method of reacting a nitrogen-containing heterocyclic compound having an amino group with a carboxylic anhydride, a method of condensing a nitrogen-containing heterocyclic compound having an amino group and a compound having an acid group such as a carboxylic acid group or a sulfonic acid group with an acid using a condensing agent such as carbodiimide, etc.

[0519] The content of the specific nitrogen-containing compound is preferably 0.01 to 5.0% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The upper limit is more preferably 2.0% by mass or less, and further preferably 1.0% by mass or less.

[0520] The specific nitrogen-containing compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

[0521] <Polymerizable Compound>

[0522] The resin composition of the present invention preferably contains a polymerizable compound.

[0523] The compound corresponding to the above-mentioned specific nitrogen-containing compound does not correspond to the polymerizable compound.

[0524] Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0525] 〔Free radical crosslinking agent〕

[0526] The resin composition of the present invention preferably contains a radical crosslinking agent.

[0527] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferably used. As the above-mentioned group containing an ethylenically unsaturated bond, groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group can be cited.

[0528] Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group. From the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0529] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

[0530] The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds.

[0531] Furthermore, from the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0532] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0533] As a specific example of a free radical crosslinking agent, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl or amino, sulfanyl groups and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reactions of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. In addition, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociable substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, the unsaturated carboxylic acid may be replaced by a compound group consisting of unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, reference may be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and these contents are incorporated into this specification.

[0534] Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include 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(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trimethylolethane, etc., to which ethylene oxide or propylene oxide is added and then (meth)acrylate is performed. Compounds obtained by esterification, such as urethane (meth) acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and polyfunctional acrylates or methacrylates and mixtures thereof. Also, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Also, polyfunctional (meth) acrylates obtained by reacting compounds having a cyclic ether group and an ethylenically unsaturated bond such as (meth) acrylate glycidyl with a polyfunctional carboxylic acid can be cited.

[0535] Furthermore, as preferred radical crosslinking agents other than the above, compounds having a fluorene ring and having two or more groups containing ethylenically unsaturated bonds, or cardo resins described in JP-A-2010-160418, JP-A-2010-129825, and JP-4364216 may be used.

[0536] In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can also be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0537] 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 the contents thereof are incorporated into the present specification.

[0538] In Japanese Patent Application Laid-Open No. 10-062986, compounds described as formula (1) and formula (2) together with specific examples thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resultant, can also be used as a radical crosslinking agent.

[0539] Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical crosslinking agents, and these contents are incorporated into the present specification.

[0540] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

[0541] Commercially available products of the radical crosslinking agent include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethyleneoxy chains; SR-209, 231, and 239 manufactured by Sartomer Company, Inc., which are bifunctional methyl acrylates having four vinyloxy chains; DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentyleneoxy chains; TPA-330 manufactured by Nippon Kayaku Co., Ltd., which is a trifunctional acrylate having three isobutyleneoxy chains; urethane oligomers UAS-10 and 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.); 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.

[0542] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0543] The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. It is particularly preferred that among the free radical crosslinking agents having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. include M-510, M-520, and the like.

[0544] The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the workability in production is excellent, and further the developability is excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

[0545] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition.

[0546] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, Acrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate having other urethane bonds, bifunctional methacrylate having urethane bonds. Two or more of these can be mixed and used as needed.

[0547] For example, PEG200 diacrylate means polyethylene glycol diacrylate, and the formula weight of the polyethylene glycol chain is about 200.

[0548] Regarding the resin composition of the present invention, from the viewpoint of suppressing warpage by controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used 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-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or more at normal pressure is also preferred.

[0549] In addition, examples of bifunctional or higher-functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

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

[0551] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[0552] 〔Other cross-linking agents〕

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

[0554] In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, and are preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products through the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products through the action of acids or bases.

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

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

[0557] As other crosslinking agents, for example, compounds having a structure in which a compound containing an amino group such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol to replace the hydrogen atom of the amino group with an acyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group can be cited. The method for producing these compounds is not particularly limited, as long as the compounds have the same structure as the compounds produced by the above method. In addition, oligomers formed by self-condensation of the hydroxymethyl groups of these compounds can also be used.

[0558] A cross-linking agent using melamine as the amino group-containing compound is referred to as a melamine-based cross-linking agent, a cross-linking agent using glycoluril, urea or alkylene urea is referred to as a urea-based cross-linking agent, a cross-linking agent using alkylene urea is referred to as an alkylene urea-based cross-linking agent, and a cross-linking agent using benzoguanamine is referred to as a benzoguanamine-based cross-linking agent.

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

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

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

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

[0563] The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.

[0564] [Chemical formula 34]

[0565]

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

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

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

[0569] [Chemical formula 35]

[0570]

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

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

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

[0574] In the formula, R 36 ~R 39 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.

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

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

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

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

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

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

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

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

[0583] Furthermore, these groups may have a known substituent within a range where the effects of the present invention can be obtained.

[0584] R01 and R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

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

[0586] As the compound having an alkoxymethyl group, specifically, the following structures can be cited. As for the compound having an acyloxymethyl group, the 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 various compounds can be cited, but are not limited to these.

[0587] [Chemical formula 36]

[0588]

[0589] [Chemical formula 37]

[0590]

[0591] As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.

[0592] 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.

[0593] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0594] Specific examples of the urea-based crosslinking agent include monomethylol glycoluril, dimethylol glycoluril, trimethylol glycoluril, tetramethylol glycoluril, monomethoxymethyl glycoluril, dimethoxymethyl glycoluril, trimethoxymethyl glycoluril, tetramethoxymethyl glycoluril, monoethoxymethyl glycoluril, diethoxymethyl glycoluril, triethoxymethyl glycoluril, tetraethoxymethyl glycoluril, monopropoxymethyl glycoluril, dipropoxymethyl glycoluril, tripropoxymethyl glycoluril, tetrapropoxymethyl glycoluril, monobutoxymethyl glycoluril, dibutoxymethyl glycoluril, tributoxymethyl glycoluril, or tetrabutoxymethyl glycoluril;

[0595] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0596] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[0597] Propylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[0598] 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0599] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0600] In addition, as the compound having at least one group selected from a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0601] Specific examples of such compounds include benzyl alcohol, 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)diphenyl Benzophenone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0602] As other crosslinking agents, commercially available products may be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0603] Furthermore, the resin composition of the present invention also preferably contains at least one compound selected from epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0604] -Epoxy compounds (compounds having epoxy groups)-

[0605] 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 a temperature below 200°C and does not produce a dehydration reaction caused by crosslinking, so it is not easy to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0606] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

[0607] Examples of epoxy compounds include: bisphenol A epoxy resin; bisphenol F epoxy resin; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these.Specific examples include EPICLON (registered trademark) 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 (these are trade names, manufactured by DICCORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, RikaResin (registered trademark) HBE-100, RikaResin (registered trademark) DME-100, RikaResin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[0608] [Chemical formula 38]

[0609]

[0610] In the formula, n is an integer of 1-5, and m is an integer of 1-20.

[0611] In the above structure, from the viewpoint of achieving both heat resistance and improvement in elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[0612] -Oxetane compound (compound having an oxetane group)-

[0613] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0614] -Benzoxazine compound (compound having a benzoxazolyl group)-

[0615] Benzoxazine compounds are preferred because they cause a crosslinking reaction by a ring-opening addition reaction, do not cause outgassing during curing, and further reduce thermal shrinkage to suppress the occurrence of warping.

[0616] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0617] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. Other crosslinking agents may contain only one or more. When containing more than two other crosslinking agents, it is preferred that the total is within the above range.

[0618] 〔Polymerization initiator〕

[0619] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat, and particularly preferably contains a photopolymerization initiator.

[0620] The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, it is preferably a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region. In addition, it can also be an activator that generates active free radicals by reacting with a photoexcited sensitizer.

[0621] The photoradical polymerization initiator preferably contains at least one photopolymerization initiator having a photopolymerization activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1 The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0622] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For details of these, it is possible to refer to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, Japanese Patent Publication No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313 can be cited, and these contents are also incorporated into this specification.

[0623] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, and the contents are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0624] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

[0625] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0626] As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0627] As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 having a maximum absorption wavelength that matches a light source having a wavelength of 365 nm or 405 nm can also be used, and this content is incorporated into the present specification.

[0628] Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

[0629] Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0630] As the photoradical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

[0631] Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science. and Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc., and the contents are incorporated into this specification.

[0632] Preferred oxime compounds include, for example, compounds of the following structures, 3-(benzoyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propionyloxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0633] [Chemical formula 39]

[0634]

[0635] Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052) can also be preferably used. In addition, 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 also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds having the following structures can also be used.

[0636] [Chemical formula 40]

[0637]

[0638] As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in JP-06636081, and the contents are incorporated into this specification.

[0639] As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring in a carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505, and the contents are incorporated into this specification.

[0640] In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, and the like, and the contents are incorporated into this specification.

[0641] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably set as a dimer. As a specific example of an oxime compound having a nitro group, the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and paragraphs 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071 can be cited, and the contents are incorporated into this specification. In addition, as an oxime compound having a nitro group, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) can also be cited.

[0642] As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0643] As a photoradical polymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to the carbazole skeleton can also be used. As such a photopolymerization initiator, compounds described in International Publication No. 2019 / 088055 can be cited, and the contents are incorporated into this specification.

[0644] As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1The electron withdrawing group possessed may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano groups, preferably acyl and nitro groups, and more preferably acyl groups, and more preferably benzoyl groups, from the perspective of easily forming a film with excellent light resistance. Benzoyl groups may have substituents. As substituents, preferably halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl, alkoxy groups, aryl, aryloxy groups, heterocyclic groups, heterocyclic oxygen groups, alkenyl groups, alkylthio groups, arylthio groups, acyl groups or amino groups, more preferably alkyl, alkoxy groups, aryl, aryloxy groups, heterocyclic oxygen groups, alkylthio groups, arylthio groups or amino groups, and more preferably alkoxy groups, alkylthio groups or amino groups.

[0645] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2).

[0646] [Chemical formula 41]

[0647]

[0648] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an 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 phosphinoyl group, a carbamoyl group or a sulfamoyl group,

[0649] R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

[0650] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0651] Among them, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0652] In the above formula, preferably R X12 is an electron-withdrawing group, R X10 , R X11 , R X13 , R X14 A hydrogen atom.

[0653] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents are incorporated into the present specification.

[0654] The most preferred oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like, and the contents are incorporated into the present specification.

[0655] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0656] Further preferred photoradical polymerization initiators are trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to use at least one compound selected from trihalomethyl triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds.

[0657] In addition, the photoradical polymerization initiator may also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, aromatic ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propanone-1, quinones formed by ring condensation of an aromatic ring such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, compounds represented by the following formula (I) may also be used.

[0658] [Chemical formula 42]

[0659]

[0660] 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 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 a phenyl or biphenyl group substituted by at least one of the following: R I01 is a group represented by formula (II) or is I00 The same group, R I02 ~R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0661] [Chemical formula 43]

[0662]

[0663] In the formula, R I05 ~R I07 R of the above formula (I) I02 ~R I04 same.

[0664] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents are incorporated into the present specification.

[0665] As the photo-radical polymerization initiator, a photo-radical polymerization initiator of difunctional or trifunctional or more can be used. By using such a photo-radical polymerization initiator, more than two free radicals are generated from one molecule of the photo-radical polymerization initiator, so good sensitivity can be obtained. And, when using a compound of asymmetric structure, crystallinity is reduced and the solubility in solvents etc. is improved, and it becomes difficult to separate out over time, thereby being able to improve the stability over time of resin combination. Specific examples of the bifunctional or trifunctional or higher-functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T 2010-527339, JP-T 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-T 2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds (E) and (G) described in JP-T 2013-522445. ), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., and the contents are incorporated into this specification.

[0666] When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. The photopolymerization initiator may contain only one or more. When containing more than two photopolymerization initiators, the total amount is preferably within the above range.

[0667] In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may further proceed by heating in an oven, a hot plate, or the like.

[0668] 〔Sensitizer〕

[0669] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat generation, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases.

[0670] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azo methine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0671] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene dihydroindanone, p-dimethylamino benzylidene dihydroindanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, diethylamino isopentyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0672] Also, other sensitizing pigments may be used.

[0673] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of JP-A-2016-027357, and the contents are incorporated into the present specification.

[0674] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and further preferably 0.5 to 10 mass % relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0675] 〔Chain transfer agent〕

[0676] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, polyols having -SS-, -SO- 2 -S-, -NO-, SH, PH, SiH and GeH compound groups, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, etc. These can generate free radicals by donating hydrogen to low-activity free radicals or can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

[0677] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0678] 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 further preferably 0.5 to 5 parts by mass relative to 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 or more than two. When the chain transfer agent is more than two, it is preferred that the total is within the above range.

[0679] 〔Photoacid generator〕

[0680] The resin composition of the present invention preferably contains a photoacid generator.

[0681] The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light of a wavelength of 300 nm to 450 nm, more preferably light of 330 nm to 420 nm. When the photoacid generator is used alone or together with a sensitizer, the photoacid generator is preferably one that can generate an acid by photosensitization.

[0682] Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonic acid amides.

[0683] Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oximesulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, and onium salt compounds.

[0684] From the viewpoint of sensitivity and storage stability, organic halogenated compounds, oxime sulfonate compounds and onium salt compounds are preferred, and from the viewpoint of mechanical properties of the formed film, etc., oxime esters are preferred.

[0685] As quinonediazide compounds, there can be mentioned compounds obtained by bonding sulfonic acid esters of quinonediazide to monovalent or polyvalent hydroxy compounds, compounds obtained by bonding sulfonic acid of quinonediazide to monovalent or polyvalent amino compounds via sulfonamide, compounds obtained by bonding sulfonic acid of quinonediazide to polyhydroxypolyamino compounds via ester bonds and / or sulfonamide, etc. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferred that 40 mol% or more of the functional groups as a whole are substituted with quinonediazide on average. By containing such quinonediazide compounds, a resin composition that is sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

[0686] Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropyl alcohol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but are not limited to these.

[0687] Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide, but are not limited thereto.

[0688] Furthermore, specific examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited thereto.

[0689] Among these, it is preferable to contain a phenol compound and an ester with 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. This can achieve higher sensitivity and higher resolution to i-ray exposure.

[0690] The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, a contrast between the exposed portion and the unexposed portion can be obtained, thereby achieving higher sensitivity, which is preferred. In addition, a sensitizer or the like may be added as needed.

[0691] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").

[0692] The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105).

[0693] [Chemical formula 44]

[0694]

[0695] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group or a halogen atom. 3 In the case of , they may be the same or different. 3 The alkyl group and alkoxy group in the above-mentioned X may have a substituent. 3 The alkyl group in is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above-mentioned X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in the formula (a) is preferably a chlorine atom or a fluorine atom.

[0696] In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 Can be the same or different.

[0697] In formula (OS-1), R 34W represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0698] In formula (OS-1), it is particularly preferred that m3 is 3, X 3 is methyl, X 3 The substitution position is ortho, R 34 A compound which is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl or p-tolyl group.

[0699] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, and the contents are incorporated herein.

[0700] [Chemical formula 45]

[0701]

[0702] In formula (OS-103) to formula (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are multiple R s2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and a plurality of R may exist. s6 Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0-6.

[0703] In formula (OS-103) to formula (OS-105), R s1 The represented alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) may have a known substituent within a range that can achieve the effects of the present invention.

[0704] In formula (OS-103) to formula (OS-105), R s2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group.s2 Among them, preferably 1 or 2 are alkyl groups, aryl groups or halogen atoms, more preferably 1 is alkyl groups, aryl groups or halogen atoms, and particularly preferably 1 is alkyl groups and the rest are hydrogen atoms. s2 The alkyl group or aryl group represented may have a known substituent within a range in which the effects of the present invention can be obtained.

[0705] In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0706] In formula (OS-103) to formula (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0707] In formula (OS-103) to formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by the above-mentioned group may have a substituent.

[0708] In formula (OS-103) to formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0709] Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).

[0710] [Chemical formula 46]

[0711]

[0712] In formula (OS-106) to formula (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R t2 represents a hydrogen atom or a methyl group.

[0713] In formula (OS-106) to formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0714] In formula (OS-106) to formula (OS-111), R t8 It represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0715] In formula (OS-106) to formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

[0716] R t2 It represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0717] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime may be any one or a mixture.

[0718] Specific examples of the oxime sulfonate compounds represented by the formula (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[0719] As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be mentioned.

[0720] [Chemical formula 47]

[0721]

[0722] In formula (OS-101) or formula (OS-L02), R u9 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. u9 More preferably, R u9 The embodiment of cyano, phenyl or naphthyl is more preferred.

[0723] In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group.

[0724] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, or -NR u5 -、-CH 2 -、-CR u6 H- or CR u6 R u7 -, R u5 ~R u7 Each independently represents an alkyl group or an aryl group.

[0725] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfone group, a cyano group or an aryl group. u1 ~R u4 The two of them can be bonded to each other to form a ring. In this case, the ring can be condensed to form a condensed ring with the benzene ring. u1 ~R u4 , preferably a hydrogen atom, a halogen atom or an alkyl group, and also preferably R u1 ~R u4 At least two of them are bonded to each other to form an aromatic group. Among them, R u1 ~R u4 All of the above substituents may further have a substituent.

[0726] The compound represented by the above formula (OS-101) is more preferably a compound represented by formula (OS-102).

[0727] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one or a mixture thereof.

[0728] Specific examples of the compound represented by formula (OS-101) include compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraphs 0195 to 0207 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[0729] Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferred.

[0730] [Chemical formula 48]

[0731]

[0732] Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0733] Furthermore, the compounds represented by the following structural formula can also be mentioned as preferred examples.

[0734] [Chemical formula 49]

[0735]

[0736] Specific examples of the organic halogenated compound include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Publication No. 48-36281, Japanese Patent Application Publication No. 55-32070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-58241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-70243, Japanese Patent Application Publication No. 63-298339, MP Hutt "Journal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., and these contents are incorporated into the present specification. In particular, trihalomethyl-substituted oxazole compounds: S-triazine compounds can be cited as preferred examples.

[0737] More preferably, there can be mentioned s-triazine derivatives obtained by bonding at least one mono-, di- or tri-halogen-substituted methyl group to the s-triazine ring, and specifically, for example, there can be mentioned 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, -s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine] s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-naphthyloxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine and the like.

[0738] Examples of the organic borate compound include Japanese Patent Application Laid-Open No. 62-143044, Japanese Patent Application Laid-Open No. 62-150242, Japanese Patent Application Laid-Open No. 9-188685, Japanese Patent Application Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., the organic borate salts described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561, the organic boron sulfonium complex or the organic boron oxysulfonium complex, the organic boron iodine complex described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553 Specific examples include the organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, and the contents are incorporated into this specification.

[0739] Examples of the disulfone compound include compounds described in Japanese Unexamined Patent Application Publication No. 61-166544, Japanese Patent Application Publication No. 2001-132318, and diazodisulfone compounds.

[0740] Examples of the onium salt compound include diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T. S. Balet al, Poymer, 21, 423 (1980), ammonium salts described in U.S. Pat. No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc., phosphonium salts described in the specifications of U.S. Pat. No. 4,069,055 and U.S. Pat. No. 4,069,056, iodine salts described in the specifications of European Patent No. 104,143, U.S. Pat. No. 339,049 and U.S. Pat. No. 410,201, Japanese Patent Application Publication No. 2-150848 and Japanese Patent Application Publication No. 2-296514, European Patent No. 370,693 and European Patent No. 3 Sulfonium salts described in the specifications of Patent No. 90,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, JV Crivello et al, Macromolecules, 10 (6), 1307 (1977), selenium salts described in JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsenic salts, onium salts such as pyridinium salts described in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and the like, and these contents are incorporated into the present specification.

[0741] Examples of the onium salt include onium salts represented by the following general formulae (RI-I) to (RI-III).

[0742] [Chemical formula 50]

[0743]

[0744] In formula (RI-I), Ar 11represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in an alkyl group, an arylamido group having 6 to 20 carbon atoms in an aryl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the perspective of stability, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, or a sulfinate ion is preferred. 21 ,Ar 22 Each independently represents an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in an alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in an alkyl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. In view of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred. In formula (RI-III), R 31 , R 32 , R 33Each independently represents an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms which may have 1 to 6 substituents, and is preferably an aryl group in view of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in an alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in an alkyl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. In view of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or a carboxylate ion is preferred.

[0745] Specific examples of preferred photoacid generators include the following.

[0746] [Chemical formula 51]

[0747]

[0748] [Chemical formula 52]

[0749]

[0750] [Chemical formula 53]

[0751]

[0752] [Chemical formula 54]

[0753]

[0754] [Chemical formula 55]

[0755]

[0756] The photoacid generator is used in an amount of preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, further preferably 0.5 to 10% by mass, further preferably 0.5 to 3% by mass, and further preferably 0.5 to 1.2% by mass based on the total solid content of the resin composition.

[0757] The photoacid generator may be used alone or in combination of two or more. When two or more photoacid generators are used in combination, the total amount thereof is preferably within the above range.

[0758] Furthermore, in order to impart photosensitivity to a desired light source, it is also preferably used together with a sensitizer.

[0759] <Alkali Generator>

[0760] 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 or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.

[0761] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali generator. When the resin composition contains a thermal alkali generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties or chemical resistance of the cured product become good, for example, the performance as an interlayer insulating film for a redistribution layer included in a semiconductor package becomes good.

[0762] The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.

[0763] There is no particular limitation on the base generating agent involved in the present invention, and a known base generating agent can be used. As a known base generating agent, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid amide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, etc. can be used.

[0764] Specific examples of the nonionic base generating agent include compounds represented by formula (B1), formula (B2) or formula (B3).

[0765] [Chemical formula 56]

[0766]

[0767] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 In addition, in this specification, the tertiary amine structure refers to a structure in which the three connecting bonds of the trivalent nitrogen atom are covalently bonded to the hydrocarbon carbon atom. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when an amide group is formed together with the nitrogen atom, it is not limited to this.

[0768] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 At least one of the rings preferably contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by 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 and a benzene ring, more preferably a cyclohexane ring.

[0769] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effect of the present invention is exerted. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The formed ring is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Particularly preferred is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group which may have a substituent.

[0770] As Rb 3, examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), aralkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and aralkyloxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). Among them, preferred are cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), arylalkenyl, and arylalkyloxy. 3 The compound may further have a substituent within a range where the effects of the present invention are exhibited.

[0771] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0772] [Chemical formula 57]

[0773]

[0774] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 have the same meaning.

[0775] R 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent within the range in which the effects of the present invention are exerted. Among them, Rb 13 An aralkyl group is preferred.

[0776] R 33 and Rb 34Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0777] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and is preferably an aryl group.

[0778] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0779] [Chemical formula 58]

[0780]

[0781] R 11 and Rb 12 With Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0782] R 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom or a methyl group.

[0783] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0784] [Chemical formula 59]

[0785]

[0786] In formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 or more. N1 and R N2 Each independently represents a monovalent organic group.

[0787] As described above, in this specification, "connection chain" refers to a chain connecting two atoms of the connection object or the connection between the atomic chains on the path between the connecting atoms in the shortest way (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the connection chain is composed of 4 carbon atoms, and the number of atoms on the path of the connection chain (that is, the number of atoms constituting the connection chain, hereinafter also referred to as "connection chain length" or "length of the connection chain") is 4.

[0788] [Chemical formula 60]

[0789]

[0790] The number of carbon atoms in L of formula (B3) (including carbon atoms other than carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, the upper limit of the length of the connecting chain of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the length of the connecting chain of L is preferably 4 or 5, and most preferably 4. As specific preferred compounds of the alkali generator, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002 can also be cited.

[0791] Furthermore, the base generating agent also preferably contains a compound represented by the following formula (N1).

[0792] [Chemical formula 61]

[0793]

[0794] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0795] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and further preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that becomes the shortest path between the two carbonyl groups in the formula.

[0796] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10), specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), preferably an aliphatic hydrocarbon group. N1 and R N2 , if an aliphatic hydrocarbon group is used, the basicity of the generated base is high, so it is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the aliphatic hydrocarbon group can be exemplified as having an oxygen atom in the hydrocarbon chain.

[0797] As a component of R N1 and R N2 Examples of the aliphatic hydrocarbon group include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0798] The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0799] The group related to the combination of a chain alkyl group and a cyclic alkyl group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and further preferably 4 to 12 carbon atoms. Examples of the group related to the combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0800] The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-shaped or cyclic, and may be linear or branched.

[0801] However, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 An alkyl group having 5 to 12 carbon atoms is preferred. Among them, in a formulation where adhesion to a metal (eg, copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0802] R N1 and R N2 They can be connected to each other to form a ring structure. When forming a ring structure, they can have oxygen atoms in the chain. N1 and R N2 The formed cyclic structure can be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. As the formed cyclic structure, it is preferably a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidinyl ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc.

[0803] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0804] The protecting group is preferably a protecting group that is decomposed by the action of an acid or a base, and preferably a protecting group that is decomposed by an acid.

[0805] As specific examples of protecting groups, chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain can be cited. As chain or cyclic alkyl groups, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. As chain alkyl groups having an oxygen atom in the chain, specifically, alkyloxyalkyl groups can be cited, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl (EE) groups, etc. can be cited. As cyclic alkyl groups having an oxygen atom in the chain, epoxy groups, glycidyl groups, oxetanyl groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc. can be cited.

[0806] As the divalent linking group constituting L, there is no particular regulation, but it is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may also have atoms of a type other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups preferably do not have an oxygen atom.

[0807] The divalent hydrocarbon linking group is preferably a group having 1 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably a group having 1 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably a group having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10. The group associated with the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., an arylene alkyl group) is preferably a group having 7 to 22 carbon atoms, more preferably 7 to 18, and further preferably 7 to 10.

[0808] Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

[0809] The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0810] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

[0811] The group related to the combination of the linear alkylene group and the cyclic alkylene group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0812] The alkylene group having an oxygen atom in the chain may be chain-shaped or cyclic and may be straight-chain or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0813] The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched alkenylene group preferably has 1 to 10 carbon=C bonds, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0814] The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The number of C═C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0815] The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms.

[0816] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.

[0817] Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, arylene groups, and alkylene groups; more preferred are 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and oxyethylene (especially 1,2-vinyloxy-1,2-ethylene).

[0818] The following examples can be cited as the alkali generating agent, but the present invention should not be construed as being restrictive thereby.

[0819] [Chemical formula 62]

[0820]

[0821] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0822] As specific 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 mentioned.

[0823] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these.

[0824] [Chemical formula 63]

[0825]

[0826] Specific examples of the imide salt include the following compounds, but the present invention is not limited to these.

[0827] [Chemical formula 64]

[0828]

[0829] When the resin composition of the present invention contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition 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, and further preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less.

[0830] The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

[0831] <Solvent>

[0832] The resin composition of the present invention preferably contains a solvent.

[0833] Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0834] Preferred examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.) ethyl 2-methoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0835] Preferred examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0836] Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, and dihydroglucosanone.

[0837] Preferred examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0838] As the sulfoxides, for example, dimethyl sulfoxide is preferably used.

[0839] As amides, preferably there are mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

[0840] Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0841] Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl phenyl carbinol, n-pentanol, methyl pentanol and diacetone alcohol.

[0842] From the viewpoint of improving the properties of the coating surface, etc., the solvent is preferably a mixture of two or more kinds.

[0843] In the present invention, it is preferred to use one solvent selected from the group consisting of 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucosanone, and dihydroglucosanone, or a mixed solvent consisting of two or more thereof. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously or to use N-methyl-2-pyrrolidone and ethyl lactate simultaneously.

[0844] Regarding the content of the solvent, from the viewpoint of coating properties, it is preferably set to an amount in which the total solid content concentration of the resin composition of the present invention becomes 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and further preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the coating method.

[0845] The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, the total amount thereof is preferably within the above range.

[0846] <Metal Adhesion Improver>

[0847] The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0848] 〔Silane coupling agent〕

[0849] Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573, and the contents thereof are incorporated into the present specification. Furthermore, 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. Furthermore, the following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0850] [Chemical formula 65]

[0851]

[0852] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0853] 〔Aluminum-based adhesive additive〕

[0854] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate aluminum diisopropoxide.

[0855] Furthermore, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and these contents are incorporated into this specification.

[0856] 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 further preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one kind or two or more kinds. When using two or more kinds, it is preferred that the total is within the above range.

[0857] <Migration Inhibitor>

[0858] The resin composition of the present invention may further contain a migration inhibitor.

[0859] The compounds corresponding to the above-mentioned specific nitrogen-containing compounds do not correspond to migration inhibitors.

[0860] By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions originating from the metal layer (metal wiring) into the film.

[0861] The migration inhibitor is not particularly limited, but includes compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0862] Alternatively, an ion capture agent that captures anions such as halogen ions may also be used.

[0863] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and these contents are incorporated into this specification.

[0864] Specific examples of the migration inhibitor include the following compounds.

[0865] [Chemical formula 66]

[0866]

[0867] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition of the present invention.

[0868] The migration inhibitor may be one or two or more. When there are two or more migration inhibitors, the total amount thereof is preferably within the above range.

[0869] <Polymerization Inhibitor>

[0870] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0871] As specific compounds of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, 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), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, 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-tetramethylpiperidinium 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinium 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Furthermore, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 can also be used, and the contents are incorporated into the present specification.

[0872] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and further preferably 0.05 to 10% by mass based on the total solid content of the resin composition of the present invention.

[0873] The polymerization inhibitor may be one or two or more. When there are two or more polymerization inhibitors, the total amount thereof is preferably within the above range.

[0874] <Acid scavenger>

[0875] In order to reduce the performance change caused by time from exposure to heating, the resin combination of the present invention preferably contains an acid capture agent. Here, the acid capture agent refers to the compound that can capture the acid by being present in the system, preferably the compound with low acidity and high pKa. As the acid capture agent, it is preferably a compound with amino, more preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc., further preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, especially preferably a secondary amine, a tertiary amine, an ammonium salt.

[0876] As the acid scavenger, preferably there can be mentioned compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. In the case of having an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodine, sulfonium, phosphonium, pyridinium, etc. and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0877] Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the acid scavenger having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tri(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodide hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As acid scavengers having a trialkylamine structure, tri(n-butyl)amine, tri(n-octyl)amine, etc. can be cited. As acid scavengers having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. can be cited. As acid scavengers having a pyridine structure, pyridine, 4-methylpyridine, etc. can be cited. As alkylamine derivatives having a hydroxyl group and / or an ether bond, ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tri(methoxyethoxyethyl)amine, etc. can be cited. As aniline derivatives having a hydroxyl group and / or an ether bond, N,N-bis(hydroxyethyl)aniline, etc. can be cited.

[0878] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N- Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, fine triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0879] These acid scavengers may be used alone or in combination of two or more.

[0880] The composition of the present invention may or may not contain an acid scavenger. When contained, the content of the acid scavenger is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0881] The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution caused by the thickening of the relief pattern over time from exposure to heat treatment, it is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0882] <Other additives>

[0883] Resin combination of the present invention can be matched with various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet light absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (such as defoamers, flame retardants, etc.) as needed within the scope of the effect of the present invention. By suitably containing these components, it is possible to adjust properties such as film properties. About these components, for example, it is possible to refer to the records of the 0183rd paragraph of Japanese Unexamined Patent Publication No. 2012-003225 (the 0237th paragraph of the corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification), the records of the 0101~0104th paragraphs, the 0107~0109th paragraphs of Japanese Unexamined Patent Publication No. 2008-250074, and these contents are incorporated in this specification. When matching these additives, it is preferred that the total amount of the solids content of the resin combination of the present invention is set to less than 3% by mass.

[0884] 〔Surfactant〕

[0885] As the surfactant, various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0886] By including a surfactant in the resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness or the liquid saving. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced and the wettability of the coated surface is improved, thereby improving the coating property of the coated surface. Therefore, it is more preferable to form a film of uniform thickness with less uneven thickness.

[0887] Examples of the fluorine-based surfactant include 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 (all manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all 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 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of Japanese Unexamined Patent Publication No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Unexamined Patent Publication No. 2011-132503, and these contents are incorporated into this specification. A block polymer can also be used as the fluorine-based surfactant. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2011-89090, and the contents thereof are incorporated herein.

[0888] The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

[0889] [Chemical formula 67]

[0890]

[0891] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0892] Fluorine-based surfactants can also use fluorine-containing polymers having ethylenically unsaturated groups in the side chains as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited, and the contents are incorporated into this specification. In addition, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC CORPORATION can be cited.

[0893] 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. In terms of uniformity of the thickness of the coating film or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

[0894] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

[0895] Examples of the hydrocarbon-based surfactant include 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, and PIONIN P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0896] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol 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 esters, and the like. Commercially available products include Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Co., Ltd.).

[0897] Specific examples of the cationic surfactant include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0898] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

[0899] The surfactant may be used alone or in combination of two or more.

[0900] 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.

[0901] 〔Higher fatty acid derivatives〕

[0902] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention so as to be unevenly present on the surface of the resin composition of the present invention during drying after coating.

[0903] Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0904] When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only one or more than two. When the higher fatty acid derivative is more than two, it is preferred that the total is within the above range.

[0905] 〔Thermal polymerization initiator〕

[0906] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, a polymerization reaction of a resin and a polymerizable compound can also be carried out, so that solvent resistance can be further improved. In addition, sometimes the above-mentioned photopolymerization initiator also has the function of initiating polymerization by heat, and sometimes can be added as a thermal polymerization initiator.

[0907] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, and the contents are incorporated into the present specification.

[0908] 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 further 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 or more than two. When containing more than two thermal polymerization initiators, the total amount is preferably within the above range.

[0909] 〔Inorganic particles〕

[0910] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0911] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[0912] The above average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

[0913] When the above measurement is difficult to perform, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.

[0914] 〔Ultraviolet light absorber〕

[0915] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, or other ultraviolet absorber may be used.

[0916] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. 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, and 2-hydroxy-4-octyloxybenzophenone. In addition, 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, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0917] Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In addition, examples of 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, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. , bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 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 and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0918] In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.

[0919] The composition of the present invention may or may not contain a UV absorber, but when contained, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.1% by mass, relative to the total solid content of the composition of the present invention.

[0920] 〔Organotitanium compounds〕

[0921] The resin composition of the present embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[0922] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0923] Specific examples of the organic titanium compound are shown in the following I) to VII):

[0924] I) Titanium chelate compound: Among them, from the viewpoint that the storage stability of the resin composition is good and a good cured pattern can be obtained, titanium chelate compounds having more than two alkoxy groups are more preferred. Specific examples are diisopropyl bis(triethanolamine) titanium, di(n-butyl alcohol)bis(2,4-pentanedione) titanium, diisopropyl bis(2,4-pentanedione) titanium, diisopropyl bis(tetramethylheptanedione) titanium, diisopropyl bis(ethyl acetoacetate) titanium, etc.

[0925] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide)], and the like.

[0926] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0927] IV) Monoalkoxy titanium compounds: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylbenzenesulfonate)titanium isopropoxide, and the like.

[0928] V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium phthalocyanine oxide, and the like.

[0929] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0930] VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0931] Among them, as the organic titanium compound, from the viewpoint of exerting better chemical resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound is preferred. In particular, bis(ethyl acetoacetate)titanium diisopropylate, tetra(n-butoxide)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0932] When an organic titanium compound is added, the amount thereof 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 amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0933] 〔Antioxidant〕

[0934] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be mentioned. Preferably, it is a compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, ADKSTAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, antioxidants may also include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, and the contents are incorporated into this specification. In addition, the composition of the present invention may contain a potential antioxidant as required. As a potential antioxidant, a compound in which the position where the antioxidant is exerted is protected by a protecting group can be cited, and a compound that exerts an antioxidant effect by heating at 100 to 250 ° C or heating at 80 to 200 ° C in the presence of an acid / base catalyst so that the protecting group is separated. As a potential antioxidant, the compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219 can be cited, and the content is incorporated into this specification. As a commercially available product of a potential antioxidant, ADEKAARKLS GPA-5001 (made by ADEKA CORPORATION) etc. can be cited.

[0935] Preferred examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0936] [Chemical formula 68]

[0937]

[0938] In the 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), R 6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and a monovalent to tetravalent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4.

[0939] The compound represented by formula (3) suppresses oxidative degradation of aliphatic groups and phenolic hydroxyl groups of the resin and can suppress metal oxidation by its rust-proofing effect on metal materials.

[0940] Since it can act on both the resin and the metal material, k is more preferably an integer of 2 to 4. 7 , alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, groups formed by combining these, etc., may also have a substituent. Among them, from the viewpoint of solubility in a developer and metal adhesion, it is preferred to have an alkyl ether group or -NH-, and from the viewpoint of interaction with a resin and metal adhesion during metal complex formation, -NH- is more preferred.

[0941] The compounds represented by the general formula (3) include the following examples, but are not limited to the following structures.

[0942] [Chemical formula 69]

[0943]

[0944] [Chemical formula 70]

[0945]

[0946] [Chemical formula 71]

[0947]

[0948] [Chemical formula 72]

[0949]

[0950] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving the elongation characteristics or the adhesion to the metal material, and by setting the addition amount to 10 parts by mass or less, for example, by interacting with the photosensitizer to improve the sensitivity of the resin composition. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, it is preferred that the total amount is within the above range.

[0951] 〔Anti-agglomerating agent〕

[0952] The resin composition of the present embodiment may contain an anti-agglomeration agent as required. Examples of the anti-agglomeration agent include sodium polyacrylate and the like.

[0953] In the present invention, the anti-aggregating agent may be used alone or in combination of two or more.

[0954] The composition of the present invention may contain an anti-aggregating agent or may not contain an anti-aggregating agent. However, when contained, the content of the anti-aggregating agent is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, relative to the total solid content of the composition of the present invention.

[0955] 〔Phenolic compounds〕

[0956] The resin composition of the present embodiment may contain phenolic compounds as required. As phenolic compounds, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X (above are trade names, Honshu Chemical Industry Co., Ltd. system), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (above are trade names, ASAHI YUKIZAI CORPORATION system) etc. can be cited.

[0957] In the present invention, the phenolic compound may be used alone or in combination of two or more.

[0958] The composition of the present invention may or may not contain a phenolic compound, but when contained, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, more preferably 0.02% by mass to 20% by mass, relative to the total solid content of the composition of the present invention.

[0959] 〔Other polymer compounds〕

[0960] Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may also be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

[0961] In the present invention, other polymer compounds may be used alone or in combination of two or more.

[0962] The composition of the present invention may or may not contain other polymer compounds, but when contained, the content of other polymer compounds is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid content mass of the composition of the present invention.

[0963] <Characteristics of Resin Composition>

[0964] The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000mm 2 / s~10,000mm 2 / s, more preferably 2,500 mm 2 / s~8,000mm 2 / s. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. 2 / s or more, for example, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000 mm 2 / s or less, a coating film with excellent coating surface morphology can be obtained.

[0965] <Regarding restrictions on substances contained in the resin composition>

[0966] The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and further preferably less than 1.0% by mass. When the water content is less than 2.0%, the storage stability of the resin composition is improved.

[0967] Examples of methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0968] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As metals, sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc. can be cited, but metals contained as complexes of organic compounds and metals are excluded. In the case of containing multiple metals, it is preferred that the total of these metals is within the above range.

[0969] Furthermore, as methods for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as 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 a device with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination, etc.

[0970] If the resin composition of the present invention is used as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the atoms present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is within the above range.

[0971] As a method for adjusting the content of halogen atoms, ion exchange treatment or the like is preferably mentioned.

[0972] As a storage container for the resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, in order to suppress the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multilayer bottle having an inner wall of the container composed of six types of six layers of resins or a bottle having a seven-layer structure of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0973] <Cured product of resin composition>

[0974] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0975] The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

[0976] 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 a film, a rod, a sphere, a granular shape, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in the form of a film. In addition, by pattern processing of the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall surface, forming a through hole (Beer Hall) for conduction, adjusting impedance or electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film formed by the cured product) is preferably 0.5μm or more and 150μm or less.

[0977] The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula.

[0978] Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[0979] <Characteristics of Cured Product of Resin Composition>

[0980] The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, the cured product may have excellent mechanical properties.

[0981] The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0982] The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[0983] <Preparation of resin composition>

[0984] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and the mixing can be performed by a conventionally known method.

[0985] The mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the pot itself, or the like.

[0986] The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0987] Furthermore, in order to remove foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to filter using a filter. Regarding the filter pore size, for example, a method of less than 5 μm can be cited, preferably less than 1 μm, more preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. In the case where the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferably used. The filter can use a filter pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can also be connected in series or in parallel for use. In the case of using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting a HDPE filter with a pore size of 1 μm as the first stage and a HDPE filter with a pore size of 0.2 μm as the second stage in series can be cited. In addition, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a circulation filter. In addition, filtering can also be performed after pressurization. When filtering under pressure, the pressure may be, for example, 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa.

[0988] In addition to filtering using a filter, an impurity removal treatment using an adsorbent may be performed. Filter filtering and impurity removal treatment using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[0989] Furthermore, after the filtration using the filter, a step of leaving the resin composition filled in the bottle under reduced pressure to deaerate the resin composition may be performed.

[0990] (Method for producing cured product)

[0991] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0992] Furthermore, the method for producing a cured product of the present invention more preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a developing step of developing the film exposed in the exposure step with a developer to form a pattern.

[0993] The method for producing a cured product of the present invention particularly preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.

[0994] Furthermore, the production method of the present invention also preferably includes the film forming step and the step of heating the film.

[0995] Hereinafter, the details of each step will be described.

[0996] <Film Formation Step>

[0997] The resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film.

[0998] The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0999] 〔Base material〕

[1000] The type of substrate can be appropriately set according to the purpose, but there is no particular limitation, and examples thereof include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, any one of a substrate formed of a metal and a substrate in which a metal layer is formed by electroplating or vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs). In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[1001] Furthermore, a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

[1002] Furthermore, the shape of the substrate is not particularly limited, and may be circular or rectangular.

[1003] The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in diameter, in the case of a circular shape, and for example, 100 to 1000 mm in length, preferably 200 to 700 mm in length of the short side in the case of a rectangular shape.

[1004] Furthermore, as the base material, for example, a plate-shaped base material (substrate) preferably a panel-shaped base material (substrate) can be used.

[1005] Furthermore, when a film is formed by applying the resin composition to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[1006] As a method of applying the resin composition of the present invention to a substrate, coating is preferred.

[1007] As the applicable method, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, inkjet, etc. can be exemplified. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating or inkjet is more preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are preferred. The solid content concentration or coating conditions of the resin composition are adjusted according to the method, so that a film of the desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, it is preferably spin coating, spray coating, inkjet, etc. If it is a rectangular substrate, it is preferably slit coating or spray coating, inkjet, etc. 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.

[1008] Furthermore, a method of transferring a coating film formed by previously applying the coating film to a temporary support by the above-mentioned applying method to a substrate can also be applied.

[1009] Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 and paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention.

[1010] Furthermore, a process of removing excess film at the end of the substrate may be performed. Examples of such a process include edge bead rinsing (EBR) and back surface rinsing (Back rinse).

[1011] Furthermore, a pre-wetting step may be adopted in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[1012] <Drying process>

[1013] The film may be subjected to a step (drying step) of drying the formed film (layer) for removing the solvent after the film forming step (layer forming step).

[1014] That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.

[1015] Furthermore, the drying step is preferably performed after the film forming step and before the exposure step.

[1016] The drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. Furthermore, drying may be performed by reducing pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[1017] <Exposure Process>

[1018] The film may be subjected to an exposure step of selectively exposing the film.

[1019] That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step.

[1020] Selective exposure means exposing a portion of the film to light, and by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.

[1021] The exposure amount is not particularly limited as long as the resin composition of the present invention ca...

Claims

1. A resin composition comprising: Cyclized resin or its precursor; and Nitrogen compounds, The nitrogen-containing compound contains a nitrogen-containing heterocycle and an amino group in the same compound, the amino group is directly bonded to the nitrogen-containing heterocycle or bonded via a hydrocarbon connecting chain, one of the hydrogen atoms of the amino group is optionally substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocycle is directly bonded to a carbonyl group, a sulfonyl group or a thiocarbonyl group.

2. The resin composition according to claim 1, wherein The nitrogen-containing heterocyclic ring comprises an imidazole skeleton, a triazole skeleton or a tetrazole skeleton.

3. The resin composition according to claim 1 or 2, wherein The amino group contained in the nitrogen-containing compound is unsubstituted.

4. The resin composition according to claim 1 or 2, wherein The length of the connecting chain between the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring and the nitrogen atom of the amino group in the nitrogen-containing compound is 3 or less.

5. The resin composition according to claim 1 or 2, wherein The nitrogen atom which is a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound is directly bonded to the carbonyl group.

6. The resin composition according to claim 1 or 2, wherein The nitrogen-containing compound is a compound represented by any of the following formula (1-1), formula (2-1) or formula (3-1); In formula (1-1), R 1 represents a monovalent organic group, R 1a Each independently represents a hydrogen atom or a substituent, R N1 represents a hydrogen atom or a substituent; In formula (2-1), R 2 represents a monovalent organic group, R 2a represents a hydrogen atom or a substituent, R N2 represents a hydrogen atom or a substituent; In formula (3-1), R 3 represents a monovalent organic group, R N3 represents a hydrogen atom or a substituent.

7. The resin composition according to claim 1 or 2, wherein The molecular weight of the nitrogen-containing compound is less than 2,000.

8. The resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film for a redistribution layer. 9 . A cured product obtained by curing the resin composition according to claim 1 . 10 . A laminate comprising two or more layers formed of the cured product according to claim 9 , and comprising a metal layer between any of the layers formed of the cured product. 11 . A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 to a substrate to form a film. 12 . The method for producing a cured product according to claim 11 , comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern. 13 . The method for producing a cured product according to claim 11 , comprising a heating step of heating the film at 50° C. to 450° C.

14. A semiconductor device comprising the cured product according to claim 9.

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