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

Abstract

To provide a resin composition excellent in storage stability of a composition, and breaking elongation of an obtained cured product, a cured product constituted by curing the resin composition, a laminate including the cured product, a production method of the cured product, and a semiconductor device including the cured product, or the laminate.SOLUTION: A resin composition includes a compound B generating a base by reaction of at least one resin selected from a group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and a base, where the compound B is represented by the following formula (1-2) or formula (1-3).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Cyclized resins such as polyimide are excellent in heat resistance, insulation, etc., and are thus applied to various uses. Although not particularly limited as the above uses, taking a semiconductor device for mounting as an example, examples include use as a material for an insulating film or a sealing material, or as a protective film. Further, it is also used as a base film or a coverlay of a flexible substrate.

[0003] For example, in the above-described uses, cyclized resins such as polyimide are used in the form of a resin composition containing a precursor of a cyclized resin such as a polyimide precursor. Such a resin composition can be applied to a substrate by, for example, coating or the like to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. The precursor of the cyclized resin such as the above polyimide precursor is cyclized by, for example, heating to become a cyclized resin such as polyimide in the cured product. Since the resin composition can be applied by a known coating method or the like, it can be said that it is excellent in manufacturing adaptability, for example, the degree of freedom in design such as the shape, size, application position, etc. of the resin composition at the time of application is high. In addition to the high performance of cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application development of the above resin composition is increasingly expected.

[0004] For example, Patent Document 1 describes a photoactive energy ray base generator characterized by having a specific urethane structure.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] In such a resin composition, improvement in both the storage stability of the composition and the elongation at break of the resulting cured product is required.

[0007] An object of the present invention is to provide a resin composition excellent in the storage stability of the composition and the elongation at break of the resulting cured product, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate.

MEANS FOR SOLVING THE PROBLEMS

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin composition containing a precursor of a cyclized resin and a compound B that generates a base by the action of a base. The resin composition containing a precursor of a cyclized resin and a compound B that generates a base by the action of a base. The resin composition. <2> The resin composition according to <1>, wherein the base generated from the compound B is an amine. <3> The resin composition according to <1> or <2>, wherein the compound B has a urethane bond. <4> The resin composition according to any one of <1> to <3>, wherein the compound B is a compound represented by the following formula (1-1), formula (1-2), or formula (1-3).

CHEMICAL FORMULA

Advantages of the Invention

[0009] According to the present invention, there are provided a resin composition excellent in storage stability of the composition and elongation at break of the obtained cured product, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, and a semiconductor device including the above cured product or the above laminate.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments. In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively. In this specification, the term "step" means not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended action of the step can be achieved. In the description of a group (atomic group) in this specification, a notation without indicating substitution and non-substitution includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent together with the group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include actinic rays or radiation such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", or either one of them; "(meth)acrylic" means both "acrylic" and "methacrylic", or either one of them; and "(meth)acryloyl" means both "acryloyl" and "methacryloyl", or either one of them. In this specification, Me in a structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the components of the composition. Also, in this specification, the solid content concentration is the mass percentage of the components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using the gel permeation chromatography (GPC) method and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and connecting in series a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) as columns. Unless otherwise stated, those molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, for example, when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Also, unless otherwise stated, detection in GPC measurement is performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when describing the positional relationship of each layer constituting a laminate as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the plurality of layers being focused on. That is, a third layer or element may further intervene between the reference layer and the other layer, and the reference layer and the other layer do not necessarily have to be in contact. Also, unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a setting of the up and down directions is for convenience in this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component as each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise stated, the temperature is 23 °C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin composition) The resin composition of the present invention contains a precursor of a cyclized resin (hereinafter, also referred to as "specific resin"), and a compound B that generates a base by the action of a base (hereinafter, simply also referred to as "compound B").

[0012] The resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used for forming a film to be subjected to development using a developer containing an organic solvent in addition to exposure. Also, the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development. In the present invention, negative development refers to development in which the unexposed portion is removed by development in exposure and development, and positive development refers to development in which the exposed portion is removed by development. As the above-described exposure method, the above-described developer, and the above-described development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the development method described in the development step are used.

[0013] The resin composition of the present invention is excellent in the storage stability of the composition and the elongation at break of the obtained cured product. Although the mechanism by which the above effects are obtained is unclear, it is presumed as follows.

[0014] Conventionally, resin compositions containing a precursor of a cyclized resin and a thermal base generator have been studied. In precursors of cyclized resins such as polyimide precursors, cyclization reactions such as imidization proceed by the action of a base. By taking advantage of this property, a film containing a resin composition having a precursor of a cyclized resin and a base generator is formed, and then a high-temperature heat treatment or the like is performed to obtain a cured product containing a cyclized resin having high heat resistance and high mechanical properties. On the other hand, it has been found that when such a composition is stored, a small amount of a basic compound may be generated in the composition liquid, and thus the cyclization reaction of the precursor of the cyclized resin may proceed in the composition. As a result, the solvent solubility of the precursor of the cyclized resin decreases, and problems such as precipitation of the above resin in the composition occur. Since cyclization is promoted under basic conditions in these precursors of cyclized resins, cyclization may be suppressed by adjusting the composition to be acidic. However, when a large amount of base is generated during storage, even if the composition is made acidic during preparation, cyclization is promoted by the action of the base in the composition. Therefore, it may be difficult to obtain the stability during storage (also referred to as the storage stability of the composition) only by adjusting the composition to be acidic. In the present invention, by using the compound B that generates a base by the action of a base, it is possible to achieve both high storage stability of the resin composition and high mechanical properties (elongation at break) of the obtained cured film. In the resin composition, Compound B has high stability and it is difficult for a base to be generated during storage, so the storage stability is high. On the other hand, during curing by heat treatment or the like, it is considered that a part of Compound B itself thermally decomposes to generate a base, or Compound B rapidly decomposes by the action of a base generated from a base generator attached separately to the resin composition to release a sufficient amount of base. As a result, it is considered that the cyclization reaction in the precursor of the cyclized resin proceeds sufficiently and high mechanical properties (elongation at break) can be realized.

[0015] Here, Patent Document 1 does not describe a resin composition containing a precursor of a cyclized resin and Compound B.

[0016] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0017] <Specific resin> The resin composition of the present invention contains a precursor of a cyclized resin (specific resin). The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain represents the relatively longest bond chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of the cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure due to heat to become a cyclized resin, and more preferably a resin that undergoes a ring closure reaction due to heat to form a ring structure and thus becomes a cyclized resin. Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, and the like. 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 a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. In addition, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, more preferably contains the radical polymerization initiator described below and a radical crosslinking agent described below. Further, if necessary, a sensitizer described below can be contained. From such a resin composition of the present invention, for example, a negative photosensitive film is formed. In addition, the specific resin may have a polarity-converting group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described below. From such a resin composition of the present invention, for example, a positive photosensitive film or a negative photosensitive film which is chemically amplified is formed.

[0018] 〔Polyimide precursor〕 The polyimide precursor used in the present invention is not particularly limited in terms of its type or the like, but preferably contains a repeating unit represented by the following formula (2).

Chemical formula

[0019] A 1 and A 2 in formula (2) each independently represents an oxygen atom or -NH-, and an oxygen atom is preferred. R 111represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a group composed of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The above linear or branched aliphatic group may be substituted with a group in which a hydrocarbon group in the chain contains a hetero atom, and the above cyclic aliphatic group and aromatic group may be substituted with a group in which a hydrocarbon group of the ring member contains a hetero atom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferable. However, Ar is independently an aromatic group, and 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-, -SO2- or -NHCO-, or a group composed of a combination of two or more of the above. These preferred ranges are as described above.

[0020] R 111 is preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds may be used. Specifically, it is preferably a diamine containing a group composed of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The above linear or branched aliphatic group may be substituted with a group in which a hydrocarbon group in the chain contains a hetero atom, and the above cyclic aliphatic group and aromatic group may be substituted with a group in which a hydrocarbon group of the ring member contains a hetero atom. Examples of the group containing an aromatic group include the following.

[0021]

Chemical formula

[0022] As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 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-hydroxyanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, 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, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl is mentioned.

[0023] Also, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferable.

[0024] Also, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 are preferably used.

[0025] R 111 From the viewpoint of the flexibility of the obtained organic film, it is preferably represented by -Ar-L-Ar-. However, 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-, -SO2- or -NHCO-, or a group composed of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0026] Also, R 111From the viewpoint of i-line transmittance, it is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61). Formula (51)

Chemical formula

Chemical formula

[0027] R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with other structures.

Chemical formula

[0028] R 115 Specifically, examples include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydrides. The polyimide precursor may contain only one type or two or more types of structures corresponding to R 115 in the form of tetracarboxylic dianhydride residues. The tetracarboxylic dianhydride is preferably represented by the following formula (O).

Chemical formula

[0029] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0030] In addition, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0031] In formula (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.

[0032] In formula (2), R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Further, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (III), etc., and a group represented by the following formula (III) is preferable.

[0033]

Chemical formula

[0034] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferable. In formula (III), * represents a bonding site with another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Examples of preferred R 201 include alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, etc., a 1,2-butanediyl group, a 1,3-butanediyl group, -CH2CH(OH)CH2-, and a polyalkyleneoxy group. Among them, alkylene groups such as an ethylene group and a propylene group, -CH2CH(OH)CH2-, a cyclohexyl group, and a polyalkyleneoxy group are more preferred, and alkylene groups such as an ethylene group and a propylene group, or a polyalkyleneoxy group are even more preferred. 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 contained in the polyalkyleneoxy group may be the same or different from each other. When the polyalkyleneoxy group contains 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, a block-containing arrangement, or an arrangement having a pattern such as an alternating pattern. The carbon number of the above alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, further more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. In addition, the above alkylene group may have a substituent. Preferred substituents include an alkyl group, an aryl group, a halogen atom, etc. In addition, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the repeating number of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6. As the polyalkyleneoxy group, from the viewpoints of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may form blocks and be arranged, or may be arranged in a pattern such as alternating. The preferable embodiments of the repeating numbers of ethyleneoxy groups and the like in these groups are as described above.

[0035] In formula (2), R 113 is a hydrogen atom, or R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0036] In formula (2), R 113 and R 114 at least one of may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

[0037] Further, it is also preferable that the polyimide precursor has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0038] Also, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there are exemplified modes such as using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0039] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A)

Chemical formula

[0040] A 1 、A 2 、R 111 、R 113 and R 114 each independently represent A in formula (2) 1 、A 2 、R 111 、R113 and R 114 is synonymous, and the preferred ranges are the same. R 112 is synonymous with R in formula (5), and the preferred ranges are the same. 112 is synonymous, and the preferred ranges are the same.

[0041] The polyimide precursor may contain one kind of repeating unit represented by formula (2), or may contain two or more kinds. Further, it may contain a structural isomer of the repeating unit represented by formula (2). Needless to say, the polyimide precursor may also contain other types of repeating units in addition to the repeating unit of the above formula (2).

[0042] As one embodiment of the polyimide precursor in the present invention, there is an aspect in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminals may be repeating units represented by formula (2).

[0043] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. The dispersity of the molecular weight of the above polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit value of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. In this specification, the dispersity of the molecular weight is a value calculated by weight average molecular weight / number average molecular weight. In addition, when the resin composition contains a plurality of polyimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the plurality of polyimide precursors as one resin are each within the above ranges.

[0044] 〔Polybenzoxazole Precursor〕 The polybenzoxazole precursor used in the present invention is not particularly defined in terms of its structure or the like, but preferably contains a repeating unit represented by the following formula (3).

Chemical Formula

[0045] In formula (3), R 123 and R 124 are synonymous with R 113 in formula (2), and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0046] As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. 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 composed of 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, still more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. 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-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula, etc.

[0047]

Chemical formula

[0048] As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid composed of only a group having the following aromatic group and two -COOH is more preferable.

[0049]

Chemical formula

[0050] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxy diphenyl ether, and terephthalic acid.

[0051] In formula (3), R 122 represents a tetravalent organic group. As the tetravalent organic group, it has the same meaning as R 115 in the above formula (2), and the preferable range is also the same. R 122is also preferably a group derived from a bisaminophenol derivative. 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'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.

[0052] Among the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic group are preferred.

[0053]

Chemical formula

[0054] The bisaminophenol derivative is preferably a compound represented by formula (A-s).

Chemical formula

[0055] In formula (A-s), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). R2 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. R3 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.

[0056]

Chemical formula

[0057] In the above formula (A-s), it is considered that having a substituent at the ortho position of the phenolic hydroxy group, that is, also on R3, can bring the carbonyl carbon of the amide bond closer to the hydroxy group, and in terms of further enhancing the effect of achieving a high cyclization rate when cured at low temperature, it is particularly preferred.

[0058] Also, in the above formula (A-s), it is preferable that R2 is an alkyl group and R3 is an alkyl group, because it can maintain the effects of high transparency to i-line and high cyclization rate when cured at low temperature.

[0059] Furthermore, in the above formula (A-s), it is more preferable that R1 is alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene related to R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, -C(CH3)2- are more preferable in that they can maintain the effects of high transparency to i-line and high cyclization rate when cured at low temperature, and can obtain a polybenzoxazole precursor with excellent balance having sufficient solubility in solvents.

[0060] As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506 can be referred to, and the contents thereof are incorporated herein.

[0061] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A No. 2013-256506, and the contents thereof are incorporated herein. Needless to say, it is not limited thereto.

[0062] The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that it can suppress the occurrence of warpage associated with ring closure.

[0063]

Chemical formula

[0064] In formula (SL), preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups. Further, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration ring closure of the polybenzoxazole precursor, suppress warpage, and achieve both the effect of improving solvent solubility.

[0065] When containing a diamine residue represented by formula (SL) as another type of repeating unit, it is also preferable to further contain a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include the examples of R 115 in formula (2).

[0066] The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably from 18,000 to 30,000, more preferably from 20,000 to 29,000, and still more preferably from 22,000 to 28,000. The number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and still more preferably from 9,200 to 11,200. The dispersity of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly defined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains a plurality of polybenzoxazole precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above ranges. Also, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the plurality of polybenzoxazole precursors as one resin are each within the above ranges.

[0067] 〔Polyamideimide precursor〕 The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

Chemical formula

[0068] In formula (PAI-2), R 117Examples include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these with a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these with a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms with a single bond or a linking group. As the above linking group, -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferred. As the above alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the above halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is even more preferred. Examples of the halogen atom in the above halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The above halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifuluoromethyl)methylene group, etc. As the above arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is even more preferred.

[0069] Also, R 117It is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. As the above halogenation, chlorination is preferable. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the above tricarboxylic acid compound, two carboxy groups may be acid anhydrified. Examples of the optionally halogenated tricarboxylic acid compound used for the production of the polyamideimide precursor include branched-chain aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0070] Specifically, as the tricarboxylic acid compound, 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 in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.

[0071] Further, specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, a compound in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or a phenylene group, and the like. These compounds may be compounds in which two carboxy groups are anhydrified (for example, trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (for example, trimellitic anhydride chloride).

[0072] In formula (PAI-2), R 111 , A 2 , R113 is respectively the R in the above formula (2) 111 , A 2 , R 113 and has the same meaning, and the preferred embodiments are the same.

[0073] The polyamideimide precursor may further contain other repeating units. Examples of the other repeating units include the repeating unit represented by the above formula (2), the repeating unit represented by the following formula (PAI-1), and the like. [Chemical formula]

[0074] In formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In formula (PAI-1), R 116 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group formed by connecting two or more of these by a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group is more preferable. Examples of the above linking group include -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferable. The above 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. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is even more preferable. Further, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferable halogenated alkylene groups include a (ditrifuluoromethyl)methylene group and the like. As the above-mentioned arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is even more preferable.

[0075] Also, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound. The carboxy group in the dicarboxylic acid dihalide compound only needs to be halogenated, but for example, it is preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound 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. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0076] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, 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 in which two or more of these are combined by a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.

[0077] In addition, 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, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, and the like. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the above dicarboxylic acid compound are halogenated.

[0078] In formula (PAI-1), R 111 is synonymous with R in the above formula (2), and the preferred embodiments are the same. 111 is synonymous with R in the above formula (2), and the preferred embodiments are the same.

[0079] Also, the polyamide-imide precursor preferably has a fluorine atom 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.

[0080] Also, for the purpose of improving the adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be mentioned.

[0081] As one embodiment of the polyamide-imide precursor in the present invention, embodiments in which the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units can be mentioned. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyamide-imide precursor excluding the terminals may be any of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2). Further, as another embodiment of the polyamideimide precursor in the present invention, there is an aspect in which 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 the repeating units. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyamideimide precursor excluding the terminals may be either the repeating unit represented by the formula (PAI-2) or the repeating unit represented by the formula (PAI-1).

[0082] 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 still more 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 still more preferably 4,000 to 25,000. The dispersity of the molecular weight of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit value of the dispersity of the molecular weight of the polyamideimide precursor is not particularly defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. Further, when the resin composition contains a plurality of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least one polyamideimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, the number average molecular weight, and the dispersity calculated as one resin for the plurality of polyamideimide precursors are within the above ranges, respectively.

[0083] 〔Method for producing polyimide precursor, etc.〕 Polyimide precursors and the like can be obtained by using methods such as reacting a tetracarboxylic dianhydride and a diamine at low temperature, reacting a tetracarboxylic dianhydride and a diamine at low temperature to obtain a polyamic acid, and esterifying using a condensing agent or an alkylating agent, obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine and a condensing agent, obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine, and so on. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting it with a diamine is more preferable. Examples of the above condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, and the like. Examples of the above alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, and the like. Examples of the above halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like. In the production method of polyimide precursors and the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and the like. In the production method of polyimide precursors and the like, it is preferable to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds. The basic compound can be appropriately determined according to the raw materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine and the like.

[0084] -Terminal capping agent- In the production method of a polyimide precursor or the like, in order to further improve the storage stability, it is preferable to block the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. When blocking the carboxylic anhydride and anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. From the viewpoints of reactivity and film stability, it is more preferable to use monoalcohol, phenols, or monoamine. Preferred compounds of monoalcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantan alcohol. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.In addition, preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more of these may be used, and by reacting a plurality of end-capping agents, a plurality of different end groups may be introduced. Also, when sealing the amino group at the resin terminal, it is possible to seal it with a compound having a functional group reactive with the amino group. Preferred sealing agents for the amino group are preferably carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and carboxylic acid anhydrides and carboxylic acid chlorides are more preferred. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. Also, preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, etc.

[0085] -Solid precipitation- In the production of polyimide precursors, etc., a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution as necessary, the obtained polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof, and the polymer component is precipitated to be precipitated as a solid and dried to obtain a polyimide precursor, etc. In order to improve the purification degree, operations such as redissolving, reprecipitating, and drying the polyimide precursor, etc. may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[0086] 〔Content〕 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, still more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Further, 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, still more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one kind of specific resin, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

[0087] Further, it is also preferable that the resin composition of the present invention contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more kinds of the specific resin and other resins described later, or may contain two or more kinds of the specific resin, but it is preferable to contain two or more kinds of the specific resin. When the resin composition of the present invention contains two or more kinds of specific resins, for example, it preferably contains two or more kinds of polyimide precursors having different structures derived from dianhydrides (R in the above formula (2)). 115

[0088] <Other resins> The resin composition of the present invention may contain the above-described specific resin and other resins different from the specific resin (hereinafter also simply referred to as "other resins"). 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, styryl resins, polyether resins, polyester resins, and the like. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, instead of, or in addition to, the polymerizable compound described below, a (meth)acrylic resin having a high polymerizable group value with a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1×10 -3 mol / g or more) is added to the resin composition, whereby the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved.

[0089] When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, still even more preferably 5% by mass or more, and still even more preferably 10% by mass or more, based on the total solid content of the resin composition. Also, in the resin composition of the present invention, the content of the other resin is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and still even more preferably 50% by mass or less, based on the total solid content of the resin composition. Also, as a preferred embodiment of the resin composition of the present invention, an embodiment in which the content of the other resin is a low content can also be adopted. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, and still even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and it may be 0% by mass or more. The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0090] <Compound B> The resin composition of the present invention contains a compound B that generates a base by the action of a base. Examples of the compound B include compounds having a basic group protected by a base-decomposable group. The basic group protected by a base-labile group is not particularly limited, and for example, a known protecting group for an amine that can be deprotected by a base can be used. For example, a group having a carbamate structure is preferable, and examples thereof include a 9-fluorenylmethylcarbamate group, a 1,1-dimethyl-2-cyanomethylcarbamate group, a paranitrobenzylcarbamate group, and a 2,4-dichlorobenzylcarbamate group.

[0091] Compound B preferably contains a urethane bond. The above urethane bond is preferably contained in the basic group protected by a base-labile group, and more preferably, the urethane bond is decomposed by the action of a base to generate an amine.

[0092] The base generated from Compound B by the action of a base is preferably an amine, and more preferably a secondary amine or a tertiary amine. In addition, the base generated from Compound B by the action of a base is preferably a base having a conjugate acid with a pKa of 0 or more, more preferably 3 or more, and still more preferably 6 or more. The lower limit of the pKa of the above conjugate acid is not particularly limited, but is preferably 30 or less. pKa is obtained by considering the dissociation reaction in which a hydrogen ion is released from an acid and expressing the equilibrium constant Ka thereof as the negative common logarithm pKa. In this specification, unless otherwise specified, the pKa is the calculated value by ACD / ChemSketch (registered trademark). When there are a plurality of pKas of the above conjugate acids, at least one of them is preferably within the above range.

[0093] The base generated from Compound B by the action of a base may be a base having only one basic group or a base having two or more basic groups. In addition, the base generated from Compound B by the action of a base may be one molecule or two or more molecules.

[0094] The molecular weight of the base generated from Compound B by the action of the base is preferably from 50 to 300, more preferably from 80 to 250.

[0095] Specific examples of the base generated are not particularly limited, and include, for example, piperidine, 4-hydroxyethylpiperidine, 4-(3-phenylpropyl)piperidine, cyclohexylamine, diisopropylamine, dicyclohexylamine, dimethylpiperidine, 1,3-di-4-piperidylpropane, 2,6-dimethylpiperidine, methylcyclohexylamine, 4-hydroxymethylpiperidine, diisobutylamine, isopropylcyclohexylamine, di-sec-isobutylamine and the like.

[0096] Compound B is preferably a compound represented by the following formula (1-1), formula (1-2) or formula (1-3), and more preferably a compound represented by the following formula (1-1).

Chemical formula

[0097] In formula (1-1), R 1 represents a hydrogen atom or a hydrocarbon group which may be substituted, and it is preferably a hydrocarbon group which may be substituted. As the above hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group is preferable, and an alkyl group or an aryl group is more preferable. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 2 to 10 carbon atoms is more preferable. The above alkyl group may be linear, branched, or cyclic, or a group represented by a combination thereof. As the above alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable. The above alkenyl group may be linear, branched, or cyclic, or a group represented by a combination thereof. As the above alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The above alkynyl group may be linear, branched, or cyclic, or a group represented by a combination thereof. As the above aryl group, an aryl group having 1 to 20 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is even more preferable. Further, the above aryl group is preferably an aromatic hydrocarbon group. As the substituent in the hydrocarbon group, known substituents can be used as long as the effects of the present invention can be obtained, and examples thereof include a hydroxy group. In formula (1-1), R 2 represents an optionally substituted hydrocarbon group. The preferred embodiment of R 2 is the same as the preferred embodiment of R 1 in the above formula (1-1). In formula (1-1), R 1 and R 2 may combine to form a ring structure. As the ring structure to be formed, a 5-membered ring or a 6-membered ring is preferred, and a 6-membered ring is more preferred. Further, the above ring structure may be an aliphatic ring structure or an aromatic ring structure, but an aliphatic ring structure is preferred. Specifically, examples of the ring structure formed by the combination of R 1 and R 2 include a piperidine ring which may have a substituent. Examples of the above substituent include an alkyl group, a hydroxyalkyl group, an aralkyl group, and the like.

[0098] In formula (1-2), the preferred embodiments of R 1 and R 2 are the same as the preferred embodiments of R 1 and R 2 in formula (1-1), respectively. In formula (1-2), each R 3 independently represents a hydrogen atom or an optionally substituted hydrocarbon group. As the above hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group is preferred, an alkyl group or an aryl group is more preferred, and an alkyl group is even more preferred. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group is even more preferred. The above alkyl group may be linear, branched, or cyclic, or a group represented by a combination thereof. As the above alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable. The above alkenyl group may be linear, branched, or cyclic, or may be a group represented by a combination thereof. As the above alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The above alkynyl group may be linear, branched, or cyclic, or may be a group represented by a combination thereof. As the above aryl group, an aryl group having 1 to 10 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is even more preferable. Further, the above aryl group is preferably an aromatic hydrocarbon group. As the substituent in the above hydrocarbon group, known substituents can be used within the range where the effects of the present invention can be obtained, and examples thereof include a hydroxy group. In formula (1-2), R 4 represents a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O)2R, a fluorinated alkyl group, or a halogen atom. From the viewpoint of the generation efficiency of the base, a cyano group is preferable. R represents an optionally substituted hydrocarbon group, and a group represented by an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, or a combination thereof is preferable, a group represented by an alkyl group, an aromatic hydrocarbon group, or a combination thereof is more preferable, and a group represented by an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group, or a combination thereof is even more preferable. Examples of the substituent in R include a halogen atom, a hydroxy group, an alkoxy group, and the like.

[0099] In formula (1-3), R 1 and R 2 preferred embodiments are the same as the preferred embodiments of R 1 and R 2 in formula (1-1), respectively. In formula (1-3), R 3 preferred embodiments are the same as the preferred embodiments of R 3 in formula (1-2). In formula (1-3), Ar represents an aromatic group substituted with at least one group selected from a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O)2R, a fluorinated alkyl group, and a halogen atom. A preferred embodiment of R is the same as R in the above formula (1-2). As the above aromatic group, an aromatic group having 1 to 20 carbon atoms is preferred, an aromatic group having 6 to 10 carbon atoms is more preferred, and a phenyl group is even more preferred. The above aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group.

[0100] Also, it is preferable to use a compound having no acid group as compound B. According to the above embodiment, migration of metals such as copper is also likely to be suppressed, and the resulting cured film is considered to have excellent adhesion.

[0101] The molecular weight of compound B is preferably 100 to 700, more preferably 100 to 500, and even more preferably 150 to 400.

[0102] Specific examples of compound B include the following compounds.

Chemical formula

Chemical formula

[0103] The content of compound B with respect to the total mass of the resin composition of the present invention is preferably 0.1 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and even more preferably 0.5 to 5.0% by mass.

[0104] <Organometallic complex> From the viewpoint of chemical resistance, the resin composition of the present invention preferably contains an organometallic complex. The organometallic complex may be any organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to the metal atom, and still more preferably a metallocene compound. In the present invention, the metallocene compound refers to an organometallic complex having two substituted or unsubstituted cyclopentadienyl anion derivatives as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferable. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0105] The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, still more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0106] The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom or two or more kinds of metal atoms.

[0107] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0108] An embodiment in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention. In the present invention, having the ability to initiate photoradical polymerization means being able to generate free radicals that can initiate radical polymerization upon irradiation with light. For example, for a composition containing a radical crosslinking agent and an organometallic complex, when irradiating light in a wavelength range where the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, the presence or absence of the ability to initiate photoradical polymerization can be confirmed by checking the presence or absence of disappearance of the radical crosslinking agent. To check the presence or absence of disappearance, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably at least one compound selected from the group consisting of a titanocene compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound and a hafnocene compound, more preferably at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound and a hafnocene compound, still more preferably at least one compound selected from the group consisting of a titanocene compound and a zirconocene compound, and particularly preferably a titanocene compound.

[0109] The molecular weight of the organometallic complex is preferably from 50 to 2,000, more preferably from 100 to 1,000.

[0110] Preferred examples of the organometallic complex include compounds represented by the following formula (P). [Chemical formula] In formula (P), M is a metal atom, and each R is independently a substituent. Each of the above R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0111] As the metal atom represented by M in formula (P), an iron atom, a titanium atom, a zirconium atom, or a hafnium atom is preferable, a titanium atom, a zirconium atom, or a hafnium atom is more preferable, a titanium atom or a zirconium atom is still more preferable, and a titanium atom is particularly preferable. Examples of the aromatic group in R in formula (P) include aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, and examples include a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. As the alkyl group in R in formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and examples include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. Examples of the halogen atom in the above R include F, Cl, Br, and I. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and examples include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. R described above may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, and the like.

[0112] Specific examples of the organometallic complex are not particularly limited, but include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compound. [Chemical formula]

[0113] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 can also be used, but are not limited thereto.

[0114] The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One or more organometallic complexes can be used. When two or more are used, the total amount is preferably within the above range.

[0115] [Solvent] The resin composition of the present invention preferably contains a solvent. As the solvent, known solvents can be arbitrarily used. Organic solvents are preferred as the solvent. Examples of the organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0116] 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 alkyl oxyacetates (e.g., methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionic acid (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkyloxypropionic acid (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-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. are preferably mentioned.

[0117] As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are mentioned as suitable ones.

[0118] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. are mentioned as suitable ones.

[0119] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and cyclic terpenes such as limonene are mentioned as suitable ones.

[0120] As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable one.

[0121] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0122] Examples of ureas include N,N,N’,N’-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0123] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol, etc.

[0124] From the perspective of improving the properties of the coating surface, it is also preferable to use a form in which two or more solvents are mixed.

[0125] In the present invention, it is preferable to use one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone, or a mixed solvent composed of two or more of them. A combined use of dimethyl sulfoxide and γ-butyrolactone, or a combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferable.

[0126] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

[0127] The resin composition of the present invention may contain only one kind of solvent or may contain two or more kinds of solvents. When two or more kinds of solvents are contained, it is preferable that the total is within the above range.

[0128] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. It is particularly preferable to contain a photoinitiator. The photoinitiator is preferably a photo radical polymerization initiator. There is no particular limitation on the photo radical polymerization initiator, and it can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Also, it may be an activator that causes some action with a photoexcited sensitizer to generate active radicals.

[0129] The photo radical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 L·mol -1 ·cm -1 in the range of about 240 to 800 nm (preferably 330 to 500 nm) in wavelength. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

[0130] As the photo radical polymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. can be mentioned. Regarding the details of these, the descriptions in paragraphs 0165 to 0182 of JP-A No. 2016-027357 and paragraphs 0138 to 0151 of WO 2015 / 199219 can be referred to, and this content is incorporated herein. Also, the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, Patent No. 6301489, the peroxide-based photoinitiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photoinitiators described in WO 2018 / 221177, the photoinitiators described in WO 2018 / 110179, the photoinitiators described in JP-A No. 2019-043864, the photoinitiators described in JP-A No. 2019-044030, and the peroxide-based initiators described in JP-A No. 2019-167313 can be mentioned, and the contents of these are also incorporated herein.

[0131] Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein. As a commercial product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0132] In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Patent No. 4225898 can be used, the content of which is incorporated herein.

[0133] Examples of the α-hydroxyketone-based initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF).

[0134] Examples of the α-aminoketone-based initiator include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF).

[0135] As the aminoacetophenone-based initiator, the compounds described in JP-A-2009-191179 in which the maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.

[0136] Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names, all manufactured by BASF) can be used.

[0137] Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0138] More preferably, the photo radical polymerization initiator includes an oxime compound. By using the oxime compound, it becomes possible to more effectively improve the exposure latitude. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

[0139] Specific examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), the compounds described in J.C.S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compounds described in JP-A-2000-066385, the compounds described in JP-T-2004-534797, the compounds described in JP-A-2017-019766, the compounds described in Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc. The contents are incorporated herein.

[0140] Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based photo radical polymerization initiator) as the photo radical polymerization initiator. The oxime-based photo radical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0141] [Chemical formula]

[0142] In commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF above), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoinitiator 2 described in JP-A-2012-014052) are also preferably used. Further, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Further, DFI-091 (manufactured by Daito Kemic Co., Ltd.), SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Further, an oxime compound having the following structure can also be used.

Chemical formula

[0143] As the photoinitiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466 and the compounds described in Patent No. 06636081, and this content is incorporated herein.

[0144] As the photoinitiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in WO2013 / 083505, and this content is incorporated herein.

[0145] In addition, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compound 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, etc., and this content is incorporated herein.

[0146] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249, paragraph numbers 0008 to 0012, 0070 to 0079 of JP-A-2014-137466, and the compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and this content is incorporated herein. In addition, as the oxime compound having a nitro group, Adeka Arcles NCI-831 (manufactured by ADEKA CORPORATION) is also included.

[0147] As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0148] As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019 / 088055, and this content is incorporated herein.

[0149] As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar OX1 into which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can also be used. The above aromatic ring group Ar OX1Examples of the electron-withdrawing group include an acyl group, nitro group, trifluoromethyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and cyano group. An acyl group and a nitro group are preferable, and an acyl group is more preferable because it easily forms a film with excellent light resistance, and a benzoyl group is even more preferable. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, cyano group, nitro group, hydroxy group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group, or amino group. An alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, or amino group is more preferable, and an alkoxy group, alkylsulfanyl group, or amino group is even more preferable.

[0150] The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).

Chemical formula

[0151] In the above formula, it is preferable that R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 are hydrogen atoms.

[0152] Specific examples of the oxime compound OX include the compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4600600, the content of which is incorporated herein.

[0153] Most preferably, the oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061, the content of which is incorporated herein.

[0154] From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivatives, a cyclopentadiene-benzene-iron complex and its salt, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound.

[0155] More preferred photoinitiators for radical polymerization are trihalomethyltriazine compounds, α - aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α - aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0156] In addition, as the photoinitiator for radical polymerization, N,N'-tetraalkyl - 4,4'-diaminobenzophenones such as benzophenone and N,N'-tetramethyl - 4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2 - benzyl - 2 - dimethylamino - 1-(4 - morpholinophenyl)-butanone - 1 and 2 - methyl - 1-[4-(methylthio)phenyl]-2 - morpholino - propanone - 1, quinones condensed with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethylketal, etc. can also be used. Further, the compound represented by the following formula (I) can also be used.

[0157]

Chemical formula

[0158] In formula (I), R I00is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group substituted by at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, and R I01 is a group represented by formula (II), or R I00 is the same group as, and R I02 ~R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0159]

Chemical formula

[0160] In the formula, R I05 ~R I07 are the same as R I02 ~R I04 in the above formula (I).

[0161] Also, as the photo radical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and this content is incorporated herein.

[0162] As the photo radical polymerization initiator, a bifunctional or trifunctional or higher-functional photo radical polymerization initiator may be used. By using such a photo radical polymerization initiator, two or more radicals are generated from one molecule of the photo radical polymerization initiator, so that good sensitivity can be obtained. Further, in the case of using a compound having an asymmetric structure, the crystallinity is lowered, the solubility in a solvent or the like is improved, and it becomes difficult to precipitate over time, and the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or higher-functional photo radical polymerization initiator include the dimer of the oxime compound described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, paragraph numbers 0407 to 0412 of JP-T-2016-532675, paragraph numbers 0039 to 0055 of WO 2017 / 033680, the compound (E) and the compound (G) described in JP-T-2013-522445, Cmpd1 to 7 described in WO 2016 / 034963, the oxime ester photoinitiator described in paragraph number 0007 of JP-T-2017-523465, the photoinitiator described in paragraph numbers 0020 to 0033 of JP 2017-167399 A, the photopolymerization initiator (A) described in paragraph numbers 0017 to 0026 of JP 2017-151342 A, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., and this content is incorporated herein.

[0163] When the photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass with respect to the total solid content of the resin composition of the present invention. The photopolymerization initiator may contain only one kind or may contain two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator in some cases, crosslinking by the photopolymerization initiator may further proceed by heating with an oven, a hot plate, or the like.

[0164] 〔Sensitizer〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., and actions such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. As the usable sensitizer, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds can be used. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-pheny-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. Regarding the details of the sensitizing dye, reference can be made to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, and this content is incorporated herein.

[0165] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0166] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683 - 684 of the Polymer Dictionary, Third Edition (edited by the Polymer Society, 2005). As the chain transfer agent, for example, a group of compounds having -S-S-, -SO2-S-, -N-O-, SH, PH, SiH, and GeH in the molecule, dithiobenzoates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, trithiocarbonates, dithiocarbamates, xanthate compounds, etc. are used. These can donate hydrogen to a low-reactivity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, a thiol compound can be preferably used.

[0167] Also, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of WO 2015 / 199219 can be used, and this content is incorporated herein.

[0168] When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass based on 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total is within the above range.

[0169] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid upon irradiation with light in the wavelength range of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. It is preferably a photoacid generator that can be sensitized to generate an acid either alone or in combination with a sensitizer. Examples of the generated acid preferably include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, hypohalous acid, sulfonamide, etc.

[0170] Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds, etc. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and oxime esters are preferred from the viewpoints of the mechanical properties of the formed film, etc.

[0171] Examples of quinonediazide compounds include those in which a sulfonic acid of quinonediazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which a sulfonic acid of quinonediazide is sulfonamide-bonded to a monovalent or polyvalent amino compound, and those in which a sulfonic acid of quinonediazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxypolyamino compound. Although not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds need to be substituted with quinonediazide, it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinonediazide. By incorporating such a quinonediazide compound, a resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

[0172] Specific examples of the hydroxy compound include, but are not limited to, phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu 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, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-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, manufactured by 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 Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-t-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.), novolak resin, etc.

[0173] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, etc.

[0174] Specific examples of the polyhydroxy polyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0175] Among these, as the quinonediazide compound, it is preferable to contain an ester with a phenol compound and a 4-naphthoquinonediazidosulfonyl group. Thereby, higher sensitivity and higher resolution with respect to i-line exposure can be obtained.

[0176] 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, based on 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, and thus higher sensitivity can be achieved, which is preferable. Further, a sensitizer or the like may be added as necessary.

[0177] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). 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), formula (OS-103), formula (OS-104), or formula (OS-105) described later.

[0178]

Chemical formula

[0179] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are a plurality of X 3 , they may be the same or different from each other. The alkyl group and the alkoxy group in the above X 3 may have a substituent. The alkyl group and the alkoxy group in the above X3 As the alkyl group in 3 , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. The above X 3 As the alkoxy group in 3 , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. The above X 3 As the halogen atom in 3 , a chlorine atom or a fluorine atom is preferred. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferred. When m3 is 2 or 3, a plurality of X 3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, and is 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 optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally 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.

[0180] In formula (OS-1), when m3 is 3, X 3 is a methyl group, the substitution position of X 3 is the ortho position, and R 34 is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group, the compound is particularly preferred.

[0181] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158 to 0167 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[0182]

Chemical formula

[0183] In Formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group, and when there are a plurality of Rs s2 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and when there are a plurality of Rs s6 each independently represents a halogen atom, an alkyl group, an alkyloxy 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 to 6. In Formulas (OS-103) to (OS-105), R s1 The 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) represented by may have known substituents within the range where the effects of the present invention can be obtained.

[0184] In Formulas (OS-103) to (OS-105), R s2 is preferably 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. When there are two or more in the compound, one or two of the Rs s2 are preferably an alkyl group, an aryl group, or a halogen atom, more preferably one is an alkyl group, an aryl group, or a halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R s2 may have known substituents within the range where the effects of the present invention can be obtained. In Formula (OS-103), Formula (OS-104), or Formula (OS-105), Xs represents O or S, and O is preferred. 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.

[0185] 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. In Formula (OS-103) to Formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by may have a substituent. In Formula (OS-103) to Formula (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0186] Also, 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).

Chemical formula

[0187] 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, 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. In Formula (OS-106) to Formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0188] In Formula (OS-106) to Formula (OS-111), 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 is 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, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0189] 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. R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Further, in the above oxime sulfonate compound, the steric structure (E, Z) of the oxime may be either one or a mixture. Specific examples of the oxime sulfonate compound represented by the above Formula (OS-103) to Formula (OS-105) include the compounds described in paragraph numbers 0088 to 0095 of JP-A-2011-209692 and paragraph numbers 0168 to 0194 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[0190] Preferable other embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following Formula (OS-101) and Formula (OS-102).

[0191]

Chemical formula

[0192] In Formula (OS-101) or Formula (OS-102), R u9represents 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. R u9 The embodiment where R is a cyano group or an aryl group is more preferable, and R u9 The embodiment where R is a cyano group, a phenyl group or a naphthyl group is even more preferable. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H-, or CR u6 R u7 -, and R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0193] In formula (OS-101) or formula (OS-102), R u1 ~R u4 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 sulfo group, a cyano group or an aryl group. R u1 ~R u4 Among them, two of them may be bonded to each other to form a ring. At this time, the ring may be fused to form a condensed ring with the benzene ring as well. R u1 ~R u4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and also, R u1 ~R u4 The embodiment where at least two of them are bonded to each other to form an aryl group is also preferable. Among them, the embodiment where R u1 ~R u4 are all hydrogen atoms is preferable. All of the above substituents may further have a substituent.

[0194] The compound represented by the above formula (OS-101) is more preferably a compound represented by formula (OS-102). In addition, in the above oximsulfonate compound, the steric structures (E, Z, etc.) of the oxime and benzothiazole ring may be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195 to 0207 of JP-A-2015-194674, and the contents thereof are incorporated herein. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred.

Chemical formula

[0195] In addition, compounds represented by the following structural formulas are also given as preferred examples.

Chemical formula

[0196] Examples of the organic halogenated compound specifically include compounds described in Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-32070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic Chemistry" 1 (No 3), (1970), etc. The contents of these are incorporated herein. In particular, oxazole compounds substituted with a trihalomethyl group and S-triazine compounds are mentioned as preferred examples. More preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 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, 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)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-i-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-naphthoxynaphthyl)-4,6-bis(trichloromethyl)-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, etc. can be mentioned.

[0197] Examples of the organic borate compound include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Patent No. 2764769, JP-A-2002-116539, etc., and organic borates described in Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”, etc., organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, organic boron iodonium complexes described in JP-A-6-175554, JP-A-6-175553, organic boron phosphonium complexes described in JP-A-9-188710, organic boron transition metal coordination complexes described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. These are given as specific examples, and the contents thereof are incorporated herein.

[0198] Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, etc. and diazodisulfone compounds.

[0199] Examples of the onium salt compound include diazonium salts described in S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056, iodonium salts described in European Patent No. 104,143, U.S. Patent Nos. 339,049 and 410,201, Japanese Patent Application Laid-Open Nos. 2-150848 and 2-296514, sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580, 3,604,581, selenonium salts described in J.V. Crivello et al, Macromolecules, 10(6), 1307 (1977), J.V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsonium salts described in C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as pyridinium salts. The contents of these are incorporated herein.

[0200] Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

Chemical formula

[0201] Specific examples of preferred photoacid generators include the following.

Chemical formula

Chemical formula

[0202] The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, still more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of two or more. In the case of a combination of two or more, the total amount thereof is preferably within the above range. In addition, in order to impart photosensitivity to a desired light source, it is also preferable to use it in combination with a sensitizer.

[0203] [Base generator] The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photo base generators. The above compound B is not included in the base generator. The resin composition of the present invention preferably contains a base generator, more preferably contains a thermal base generator or a photo base generator, and still more preferably contains a thermal base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. For example, the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package becomes good. The base generator may be an ionic base generator or a non-ionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base generator according to the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific compounds of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

Chemical formula

[0204] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Also, Rb 1 , Rb 2 and Rb 3 do not all have a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon-based carbon atoms. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom.

[0205] In formula (B1), (B2), Rb 1 , Rb 2 and Rb 3It is preferable that at least one of these contains a cyclic structure, and more preferably at least two contain a cyclic structure. The cyclic structure may be either a monocyclic or a fused ring, and a monocyclic ring or a fused ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

[0206] More specifically, Rb 1 and Rb 2 are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). These groups may have substituents within the range where the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb 1 and Rb 2 are particularly preferably a linear, branched, or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and still more preferably a cyclohexyl group which may have a substituent.

[0207] Rb 3Examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), or an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). Among them, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. Rb 3 may further have a substituent within the range where the effects of the present invention are exhibited.

[0208] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

Chemical formula

[0209] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1). Rb 13is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and may have a substituent within the scope where the effects of the present invention are exhibited. Among them, Rb 13 is preferably an arylalkyl group.

[0210] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0211] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and an aryl group is preferred.

[0212] The compound represented by the formula (B1-1) is also preferably the compound represented by the formula (B1-1a).

Chemical formula

[0213] Rb 11 and Rb 12is Rb in formula (B1-1) 11 and Rb 12 are synonymous. Rb 15 and Rb 16 is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferred. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and among them, an aryl group is preferred.

[0214] [Chemical formula]

[0215] In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. Also, R N1 and R N2 each independently represent a monovalent organic group.

[0216] In this specification, the "linking chain" refers to the atomic chain on the path connecting between two atoms or atomic groups to be linked, which connects these two objects to be linked with the shortest (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group, has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4.

Chem.

[0217] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking 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 allowing the intramolecular cyclization reaction to proceed rapidly, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraph numbers 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018 / 038002.

[0218] Also, it is preferable that the base generator contains a compound represented by the following formula (N1).

Chem.

[0219] In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0220] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As the upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest path between two carbonyl groups in the formula.

[0221] In formula (N1), R N1 and R N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms). Specifically, examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used for R N1 and R N2 the basicity of the generated base is preferably high. Note that the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have substituents, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0222] R N1 and R N2Examples of the aliphatic hydrocarbon group that constitutes the group include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain 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 even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, an isohexyl group, and the like. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. The group related to the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more 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 a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group, and the like. 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 linear or cyclic, and may be linear or branched. Among them, from the viewpoint of increasing the boiling point of the decomposition-generated base described later, R N1 and R N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a formulation that emphasizes the adhesion when laminating with a metal (for example, copper) layer, it is preferably a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms.

[0223] R N1 and R N2They may be connected to each other to form a cyclic structure. When forming a cyclic structure, it may have an oxygen atom or the like in the chain. Also, R N1 and R N2 The cyclic structure formed may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the cyclic structure to be formed, a 5-membered ring or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. For example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. may be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring are preferably mentioned.

[0224] R C1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferred.

[0225] As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is preferably mentioned.

[0226] Specific examples of the protecting group include a linear or cyclic alkyl group or a linear or cyclic alkyl group having an oxygen atom in the chain. Examples of the linear or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. Specific examples of the linear alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, etc. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group, etc.

[0227] The divalent linking group L is not particularly defined, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have a substituent, and may also have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, a divalent aliphatic hydrocarbon group which 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 which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is even more preferred. These groups preferably do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0228] Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain 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, and an arylenealkylene group. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The group related to a combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be linear 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.

[0229] The linear or branched chain 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 number of C=C bonds in the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. 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. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. 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. Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylenealkylene group are preferable, and a 1,2-ethylene group, a propanediyl group (especially 1,3-propanediyl group), a cyclohexanediyl group (especially 1,2-cyclohexanediyl group), a vinylene group (especially cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (especially 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

[0230] Examples of the base generator include the following, but the present invention is not construed as being limited thereto.

[0231]

Chemical formula

[0232] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

[0233] Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018 / 038002.

[0234] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

Chemical formula

[0235] Specific examples of the iminium salt include the following compounds, but the present invention is not limited thereto.

Chemical formula

[0236] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, may be 5 parts by mass or less, and may be 4 parts by mass or less. One kind or two or more kinds of base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0237] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent or other crosslinking agents.

[0238] [Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include 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. Among these, as the group containing an ethylenically unsaturated bond, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

[0239] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is still more preferable. Also, from the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0240] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0241] Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof. Preferably, they are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, instead of the above unsaturated carboxylic acids, it is also possible to use a group of compounds replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can refer to the descriptions in paragraphs 0113 to 0122 of JP-A-2016-027357, and these contents are incorporated herein.

[0242] In addition, 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(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerin and trimethylolethane and then (meth)acryloylating them, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-B-52-030490, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Also included are polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate.

[0243] In addition, as other preferable radical crosslinking agents, compounds having a fluorene ring and having two or more groups having an ethylenically unsaturated bond, as described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216, etc., and cardo resins can also be used.

[0244] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. Sho 46-043946, Japanese Examined Patent Publication No. Hei 01-040337, Japanese Examined Patent Publication No. Hei 01-040336, vinylphosphonic acid-based compounds described in Japanese Unexamined Patent Application Publication No. Hei 02-025493, etc. can also be mentioned. In addition, compounds containing a perfluoroalkyl group described in Japanese Unexamined Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in Journal of the Adhesion Society of Japan, vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

[0245] In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and the contents thereof are incorporated herein.

[0246] In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acryloylating them, which are described in Japanese Unexamined Patent Application Publication No. Hei 10-062986 together with their specific examples as formula (1) and formula (2), can also be used as radical crosslinking agents.

[0247] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Unexamined Patent Application Publication No. 2015-187211 can also be used as radical crosslinking agents, and the contents thereof are incorporated herein.

[0248] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue are preferred. These oligomer types can also be used.

[0249] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having 4 ethyleneoxy chains, manufactured by Sartomer Co., SR-209, 231, 239, bifunctional methacrylates having 4 ethyleneoxy chains, manufactured by Sartomer Co., DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Brenmer PME400 (manufactured by NOF Corporation), and the like.

[0250] As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Laid-Open No. Sho 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Sho 62-039417, and Japanese Patent Publication No. Sho 62-039418 are also suitable. Further, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Patent Laid-Open No. Sho 63-277653, Japanese Patent Laid-Open No. Sho 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 can also be used.

[0251] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The 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 radical crosslinking agent having an acid group by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferably, in the radical crosslinking agent having an acid group by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0252] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. If the acid value of the radical crosslinking agent is within the above range, it is excellent in handling properties during production, and furthermore, excellent in developability. Also, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

[0253] From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, modified isocyanuric acid dimethacrylate, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. These can be mixed and used in combination of two or more as needed. Note that, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200. From the perspective of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), as the radical crosslinking agent, a monofunctional radical crosslinking agent can preferably be used in the resin composition of the present invention. Examples of the monofunctional radical crosslinking agent include (meth)acrylic acid derivatives such as 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-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 °C or higher under normal pressure is also preferable in order to suppress volatilization before exposure. In addition, examples of the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0254] When the radical crosslinking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0255] The radical crosslinking agent may be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

[0256] 〔Other Crosslinking Agents〕 The resin composition of the present invention preferably contains other crosslinking agents different from the above-described radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having a plurality of groups in the molecule that promote a reaction to form a covalent bond between other compounds in the composition or their reaction products by the photosensitivity of the above-mentioned photoacid generator or photobase generator. Compounds having a plurality of groups in the molecule that promote a reaction to form a covalent bond between other compounds in the composition or their reaction products by the action of an acid or a base are preferred. The above acid or base is preferably an acid or a base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group are preferred, and compounds having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, or an alkoxymethyl group can be mentioned. The production method of these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea, or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and more preferably contains at least one compound selected from the group consisting of a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described later.

[0257] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the following urea structure, or a triazine. The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the acyloxymethyl group of the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.

[0258]

Chemical formula

[0259] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

[0260] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

[0261]

Chemical formula

[0262] In the formula, X represents a single bond or a divalent organic group, and each individual R 104 independently represents an alkyl group or an acyl group, and R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that leaves by the action of an acid, -C(R4 )2COOR 5 A group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid.)) is shown. 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. A group that decomposes by the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, -C(R 4 )2COOR 5 For R in the group represented by 5 , for example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) and the like can be mentioned. In the formula, R 36 ~R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above alkyl group may be either linear or branched. As the above cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the above aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above aralkyl group is intended to be an aryl group substituted by an alkyl group, and the preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the above alkyl groups and aryl groups. As the above alkenyl group, an alkenyl group having 3 to 20 carbon atoms is preferable, and an alkenyl group having 3 to 16 carbon atoms is more preferable. Also, these groups may further have known substituents within the range where the effects of the present invention can be obtained.

[0263] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0264] As the group that decomposes by the action of an acid to generate an alkali-soluble group, or the group that is eliminated by the action of an acid, preferably, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are mentioned. More preferably, a tertiary alkyl ester group and an acetal group are mentioned.

[0265] Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or an acyloxymethyl in the molecule include the following compounds, but are not limited thereto.

[0266]

Chemical formula

[0267]

Chemical formula

[0268] Compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group may be those commercially available or those synthesized by known methods. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0269] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like.

[0270] Specific examples of the urea-based crosslinking agent include, for example, glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as bis-methoxymethylurea, bis-ethoxymethylurea, bis-propoxymethylurea, bis-butoxymethylurea, etc. Ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated 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, Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0271] Specific examples of benzoguanamine crosslinking agents include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

[0272] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethyl benzoate hydroxymethyl phenyl, bis(hydroxymethyl)biphenyl, dimethyl bis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethyl benzoate methoxymethyl phenyl, bis(methoxymethyl)biphenyl, dimethyl bis(methoxymethyl)biphenyl, 4,4’,4’’-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5’-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3’,5,5’-tetrakis(methoxymethyl)-1,1’-biphenyl-4,4’-diol, and the like.

[0273] Commercially available products may be used as other crosslinking agents. Preferred commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Niclac (registered trademark, the same hereinafter) MX-290, Niclac MX-280, Niclac MX-270, Niclac MX-279, Niclac MW-100LM, Niclac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0274] Further, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

[0275] - Epoxy compound (compound having an epoxy group) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or lower and no dehydration reaction due to crosslinking occurs, film shrinkage is less likely to occur. Therefore, containing an epoxy compound is effective for low-temperature curing and warpage suppression of the resin composition of the present invention.

[0276] The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus can be further decreased and warping can be suppressed. The polyethylene oxide group means one having a repeating unit number of ethylene oxide of 2 or more, and preferably has a repeating unit number of 2 to 15.

[0277] Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane, etc., but are not limited thereto.Specifically, Epiklon® 850-S, Epiklon® HP-4032, Epiklon® HP-7200, Epiklon® HP-820, Epiklon® HP-4700, Epiklon® HP-4770, Epiklon® EXA-830LVP, Epiklon® EXA-8183, Epiklon® EXA-8169, Epiklon® N-660, Epiklon® N-665-EXP-S, Epiklon® N-740 (the above are product names, manufactured by DIC Corporation), Recalex® BEO-20E, Recalex® BEO-60E, Recalex® HBE-100, Recalex® DME-100, Recalex® L-200 (product name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA Corporation), Celoxide® 2021P, Celoxide® 2081, Celoxide® 2000, EHPE3150, Epolide® GT401, Epolide® PB4700, Epolide® PB3600 (the above are product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), and the like. Further, the following compounds are also preferably used.

[0278] [Chemical formula]

[0279] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0280] Among the above structures, from the viewpoint of achieving both heat resistance and improved elongation, it is preferable that n is 1 to 2 and m is 3 to 7.

[0281] - Oxetane compound (compound having an oxetanyl group) - Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3 - ethyl - 3 - hydroxymethyloxetane, 1,4 - bis{[(3 - ethyl - 3 - oxetanyl)methoxy]methyl}benzene, 3 - ethyl - 3-(2 - ethylhexylmethyl)oxetane, 1,4 - benzenedicarboxylic acid - bis[(3 - ethyl - 3 - oxetanyl)methyl]ester, etc. As specific examples, the Aron Oxetane series (for example, 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.

[0282] - Benzoxazine compound (compound having a benzoxazolyl group) - The benzoxazine compound is preferable because no degassing occurs during curing due to the cross - linking reaction derived from the ring - opening addition reaction, and furthermore, the heat shrinkage is reduced and the occurrence of warpage is suppressed.

[0283] Preferable examples of the benzoxazine compound include P - d type benzoxazine, F - a type benzoxazine (the above are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolak type dihydrobenzoxazine compounds. These can be used alone or in combination of two or more.

[0284] The content of other cross - linking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass based on the total solid content of the resin composition of the present invention. Other cross - linking agents may contain only one kind or two or more kinds. When containing two or more kinds of other cross - linking agents, the total is preferably within the above range.

[0285] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used for electrodes, wirings, 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, phosphate derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0286] 〔Silane coupling agent〕 Examples of the silane coupling agent include compounds described in paragraph 0167 of WO 2015 / 199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, compounds described in paragraphs 0063 to 0071 of WO 2011 / 080992, compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, compounds described in paragraph 0055 of WO 2014 / 097594, and compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, and the contents thereof are incorporated herein. Also, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0287]

Chemical formula

[0288] Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0289] 〔Aluminum-based adhesion promoter〕 Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

[0290] In addition, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and the contents of these are incorporated herein.

[0291] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it to be not less than the above lower limit value, the adhesion between the pattern and the metal layer becomes good, and by setting it to be not more than the above upper limit value, 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 two or more kinds are used, it is preferable that the total is within the above range.

[0292] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

[0293] 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 and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, 5-amino-1H-tetrazole can be preferably used.

[0294] Alternatively, an ion trap agent that captures anions such as halogen ions can also be used.

[0295] Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, compounds described in paragraph 0052 of JP-A-2011-059656, compounds described in paragraphs 0114, 0116, and 0118 of JP-A-2012-194520, compounds described in paragraph 0166 of WO 2015 / 199219, etc. The contents of these are incorporated herein.

[0296] Specific examples of the migration inhibitor include the following compounds.

[0297]

Chemical formula

[0298] 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 still more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition of the present invention.

[0299] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total thereof is preferably within the above range.

[0300] <Polymerization inhibitor> 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 free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, metal compounds, etc.

[0301] Specific compounds of the polymerization inhibitor include 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(I) salt, N-nitros-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitros-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitros-N-phenylhydroxylamine aluminum salt, N-nitros-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Further, 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 this content is incorporated herein.

[0302] 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 still more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

[0303] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, it is preferable that the total thereof is within the above range.

[0304] <Acid scavenger> In order to reduce the change in performance over time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Here, the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having a low acidity and a high pKa. As the acid scavenger, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt are preferable, and a secondary amine, a tertiary amine, an ammonium salt are more preferable. Examples of the acid scavenger preferably include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, aniline derivatives having a hydroxyl group and / or an ether bond, and the like. When having an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc. and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0305] Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. Examples of the acid scavenger having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. Examples of the acid scavenger having a trialkylamine structure include tri(n-butyl)amine, tri(n-octyl)amine, etc. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine, etc. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, etc. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline, etc.

[0306] 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 (diazabicycloundecene), 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, spermidine, 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, and the like.

[0307] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When it contains an acid scavenger, 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.

[0308] The usage ratio of the acid generator to the acid scavenger is preferably such that acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time until the heat treatment after exposure, it is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[0309] <Other additives> Within the range where the effects of the present invention can be obtained, the resin composition of the present invention can be blended with various additives as required, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (such as defoaming agents, flame retardants, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components can refer to, for example, the descriptions in paragraph numbers 0183 and subsequent of JP-A-2012-003225 (paragraph numbers 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraph numbers 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, and these contents are incorporated herein. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0310] 〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0311] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating solution can be further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when forming a film using a coating solution to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating solution is reduced, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is improved. For this reason, it is possible to more preferably form a film having a uniform thickness with little thickness unevenness.

[0312] Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Limited), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1-068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like. As the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used, and the contents thereof are incorporated herein. A block polymer can also be used as the fluorosurfactant, and specific examples include, for example, the compounds described in JP-A-2011-89090, and the contents thereof are incorporated herein. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [Chem.]

[0313] The weight-average molecular weight of the above compound is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the content of which is incorporated herein. Commercially available products include, for example, Megafac RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation.

[0314] The fluorine content in the fluorosurfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. The fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the coating film thickness and the liquid-saving property, and also has good solubility in the composition.

[0315] 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, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie GmbH), etc.

[0316] Examples of hydrocarbon surfactants include, for example, Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (manufactured by Takemoto Yushi Co., Ltd.), and the like.

[0317] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (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, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0318] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.), etc.

[0319] Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

[0320] Only one type of surfactant may be used, or two or more types may be combined. 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.

[0321] 〔Higher fatty acid derivative〕 In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may be added with higher fatty acid derivatives such as behenic acid and behenic acid amide, and unevenly distributed on the surface of the resin composition of the present invention during the drying process after coating.

[0322] Also, as the higher fatty acid derivative, the compounds described in paragraph 0155 of WO2015 / 199219 can also be used, and this content is incorporated herein.

[0323] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more types of higher fatty acid derivatives, the total thereof is preferably within the above range.

[0324] 〔Thermal polymerization initiator〕 The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be advanced, so that the solvent resistance can be further improved. In addition, the above-described photoinitiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0325] As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554 can be mentioned, and this content is incorporated herein.

[0326] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass based on the total solid content of the resin composition of the present invention. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0327] 〔Inorganic particles〕 The resin composition of the present invention may contain inorganic particles. As the inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

[0328] The average particle diameter of the above inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume average particle diameter. The volume average particle diameter can be measured by the dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurement is difficult, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, or the laser diffraction / scattering method.

[0329] 〔Ultraviolet absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate, etc. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0330] Examples of the substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, examples of the triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine, and the like.

[0331] In the present invention, each of the above various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When it contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[0332] [Organic Titanium Compound] The resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0333] Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like. II) Tetraalkoxytitanium compound: 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-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compound: For example, pentamethylcyclopentadienyltitanium 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, and the like. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyltridodecylbenzenesulfonyl titanate, etc.

[0334] Among them, as the organic titanium compound, it is preferable that it is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferable.

[0335] When blending the organic titanium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0336] 〔Antioxidant〕 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 a metal material can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Further, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, a phosphorus-based antioxidant can also be preferably used. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzod[f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzod[f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Examples of commercially available products of the antioxidant include, for example, AdekaStab AO-20, AdekaStab AO-30, AdekaStab AO-40, AdekaStab AO-50, AdekaStab AO-50F, AdekaStab AO-60, AdekaStab AO-60G, AdekaStab AO-80, AdekaStab AO-330 (all manufactured by ADEKA CORPORATION), and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and this content is incorporated herein. Further, the composition of the present invention may contain a latent antioxidant as necessary. Examples of the latent antioxidant include compounds in which a site functioning as an antioxidant is protected by a protecting group, and the protecting group is eliminated by heating at 100 to 250 °C or heating at 80 to 200 °C in the presence of an acid / base catalyst to function as an antioxidant.Examples of the potential anti-oxidants include the compounds described in WO 2014 / 021023, WO 2017 / 030005, and JP 2017-008219 A, the content of which is incorporated herein. Examples of commercially available products of the potential anti-oxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA CORPORATION). Examples of preferred anti-oxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

[0337]

Chemical formula

[0338] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0339] The compound represented by formula (3) suppresses the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of the resin. Further, the rust prevention effect on the metal material can suppress metal oxidation.

[0340] Since it can act on the resin and the metal material simultaneously, k is more preferably an integer of 2 to 4. R 7Examples include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, etc., and they may further have substituents. Among these, from the viewpoints of solubility in a developer and metal adhesion, it is preferable to have an alkyl ether group and -NH-, and -NH- is more preferable from the viewpoints of interaction with a resin and metal adhesion due to metal complex formation.

[0341] Examples of the compound represented by the general formula (3) include, but are not limited to, the following structures.

[0342]

Chemical formula

[0343]

Chemical formula

[0344]

Chemical formula

[0345]

Chemical formula

[0346] The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 part by mass or more, the effects of improving the elongation characteristics and adhesion to a metal material can be easily obtained even in a high-temperature and high-humidity environment. Also, by setting it to 10 parts by mass or less, for example, due to the interaction with a photosensitive agent, the sensitivity of the resin composition is improved. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that their total amount is within the above range.

[0347] 〔Anti - agglomeration agent〕 The resin composition of this embodiment may contain an anti - agglomeration agent as required. Examples of the anti - agglomeration agent include sodium polyacrylate and the like.

[0348] In the present invention, one kind of anti - agglomeration agent may be used alone, or two or more kinds may be used in combination. The composition of the present invention may or may not contain an anti - agglomeration agent. When it contains an anti - agglomeration agent, the content of the anti - agglomeration agent is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[0349] 〔Phenolic compound〕 The resin composition of this embodiment may contain a phenolic compound as required. Examples of the phenolic compound include Bis - Z, BisP - EZ, TekP - 4HBPA, TrisP - HAP, TrisP - PA, BisOCHP - Z, BisP - MZ, BisP - PZ, BisP - IPZ, BisOCP - IPZ, BisP - CP, BisRS - 2P, BisRS - 3P, BisP - OCHP, methylene tris - FR - CR, BisRS - 26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP - PC, BIR - PC, BIR - PTBP, BIR - BIPC - F (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), etc.

[0350] In the present invention, one kind of phenolic compound may be used alone, or two or more kinds may be used in combination. The composition of the present invention may or may not contain a phenolic compound. When it contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition of the present invention.

[0351] 〔Other polymer compounds〕 Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified products into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups are introduced.

[0352] In the present invention, the other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When contained, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the composition of the present invention.

[0353] <Properties of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 3,000 mm 2 / s to 8,000 mm 2 / s is even more preferable. Within the above range, it becomes easy to obtain a coating film with high uniformity. If it is less than 1,000 mm 2 / s, for example, it is difficult to coat with the film thickness required for an insulating film for rewiring. If it is 12,000 mm 2 / s or more, the coating surface condition may deteriorate.

[0354] The amount of acid groups contained in the composition per 1 g of the resin composition of the present invention (also referred to as "resist acid value") is preferably 6.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less. The lower limit of the amount of the above acid groups is not particularly limited and may be 0 mgKOH / g. Examples of the acid group include acid groups with a pKa of 15 or less, such as carboxy groups and phenolic hydroxy groups. The resist acid value is measured, for example, by a titration method using potassium hydroxide. Since the resin composition of the present invention contains compound B with excellent stability, even if the amount of the acid group is reduced, it has excellent storage stability. That is, it is not always necessary to adjust the composition to be acidic for improving the storage stability of the composition.

[0355] <Restrictions on the substances contained in the resin composition> 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 still more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0356] 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 still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., excluding metals contained as complexes of organic compounds and metals. When a plurality of metals are contained, the total of these metals is preferably within the above range.

[0357] Examples of the method for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and distilling under conditions where the inside of the apparatus is lined with polytetrafluoroethylene or the like to suppress contamination as much as possible.

[0358] Considering the use as a semiconductor material, the halogen atom content of the resin composition of the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and still more preferably less than 200 ppm by mass from the viewpoint of wiring corrosiveness. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom, or the total of the chlorine ion and the bromine ion is within the above range, respectively. As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferably mentioned.

[0359] As the storage container of the resin composition of the present invention, a conventionally known storage container can be used. Further, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 types of resins in 6 layers, or a bottle in which 6 types of resins are in a 7-layer structure. Examples of such a container include the container described in JP-A-2015-123351.

[0360] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of this resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The curing of the resin composition is preferably by heating, more preferably within the range of 120°C to 400°C, still more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as film form, rod form, spherical form, pellet form, etc. In the present invention, this cured product is preferably in film form. Also, by pattern processing of the resin composition, the shape of this cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat dissipation function. The film thickness of this cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition and can be calculated from the following formula. Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0361] <Properties of the cured product of the resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

[0362] <Preparation of the resin composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by a conventionally known method. Mixing can adopt mixing by stirring blades, mixing by ball mills, mixing by rotating the tank itself, etc. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0363] Also, for the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. Examples of the filter pore diameter include a mode of 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters with different pore diameters or materials may be combined and used. As a connection mode, for example, a mode in which an HDPE filter with a pore diameter of 1 μm is used as the first stage and an HDPE filter with a pore diameter of 0.2 μm is used as the second stage and connected in series can be mentioned. Also, various materials may be filtered multiple times. When filtering multiple times, it may be a circulating filtration. Also, filtration may be performed under pressure. When performing filtration under pressure, the pressure for pressurization is, for example, a mode of 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and still more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. A combination of filter filtration and an impurity removal treatment using an adsorbent may also be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and subjected to a degassing step.

[0364] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. Furthermore, the method for producing a cured product of the present invention more preferably includes the above film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern. The method for producing a cured product of the present invention particularly preferably includes at least one of the above film forming step, the above exposure step, the above development step, a heating step of heating the pattern obtained by the development step, and a post-exposure step of exposing the pattern obtained by the development step. Also, the production method of the present invention preferably includes the above film forming step and a step of heating the above film. Hereinafter, the details of each step will be described.

[0365] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying it onto a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.

[0366] 〔Substrate〕 The type of the substrate can be appropriately determined according to the application. Examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, and metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed of metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDP), etc., and there are no particular restrictions. In the present invention, particularly, semiconductor manufacturing substrates are preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. In addition, layers such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates. In addition, the shape of the substrate is not particularly limited, and it may be circular or rectangular. As for the size of the substrate, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm. In addition, as the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

[0367] In addition, when forming a film by applying a resin composition on the surface of a resin layer (for example, a layer made of a cured product) or a metal layer, the resin layer or the metal layer serves as a substrate.

[0368] As a means for applying the resin composition of the present invention onto a substrate, coating is preferable.

[0369] Specific examples of the application means include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is more preferable, and spin coating method and slit coating method are preferable from the viewpoints of the uniformity of the film thickness and productivity. By adjusting the solid content concentration and coating conditions of the resin composition according to the method, a film with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating method, spray coating method, inkjet method, etc. are preferable, and for a rectangular substrate, slit coating method, spray coating method, inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Further, a method of transferring a coating film previously formed by applying it on a temporary support by the above-described applying method onto a substrate can also be applied. Regarding the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096 to 0108 of JP-A-2006-047592 can also be preferably used in the present invention. Also, a step of removing an excess film may be performed at the end of the substrate. Examples of such steps include edge bead rinse (EBR), back rinse, and the like. Further, a pre-wet step may be employed in which various solvents are applied to the substrate before applying the resin composition, and the resin composition is applied after improving the wettability of the substrate.

[0370] <Drying step> The above-mentioned film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film formation step (layer formation step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film formation step. Further, the above drying step is preferably performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70°C to 130°C, and still more preferably 90°C to 110°C. Further, drying may be performed under reduced pressure. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0371] <Exposure step> The above-mentioned film may be subjected to an exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film formation step. Selectively exposing means exposing a part of the film. Further, by selectively exposing, an exposed region (exposed portion) and an unexposed region (unexposed portion) are formed in the film. The exposure amount is not particularly defined as long as the resin composition of the present invention can be cured. For example, in terms of exposure energy conversion at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm 2 is preferable, and 200 to 8,000 mJ / cm 2 is more preferable.

[0372] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and preferably 240 to 550 nm.

[0373] In terms of the relationship with the light source, the exposure wavelength includes (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i lines), (4) excimer lasers, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) the second harmonic 532 nm and the third harmonic 355 nm of YAG lasers, etc. For the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by the i-line is preferable. Thereby, particularly high exposure sensitivity can be obtained. Also, the exposure method is not particularly limited, and any method may be used as long as at least a part of the film made of the resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure by the laser direct imaging method.

[0374] <Post-exposure baking process> The above film may be subjected to a process of heating after exposure (post-exposure baking process). That is, the method for producing the cured product of the present invention may include a post-exposure baking process of heating the film exposed in the exposure process. The post-exposure baking process can be performed after the exposure process and before the development process. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Also, the heating rate may be appropriately changed during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. Also, during heating, it is also preferable to perform it in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0375] <Development step> The above-mentioned film after exposure may be subjected to a development step of forming a pattern by developing it with a developer. That is, the method for producing the cured product of the present invention may include a development step of developing the film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed. Here, development in which the non-exposed portion of the film is removed by the development step is called negative development, and development in which the exposed portion of the film is removed by the development step is called positive development.

[0376] 〔Developer〕 Examples of the developer used in the development step include an aqueous alkali solution or a developer containing an organic solvent.

[0377] When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferred is TMAH. When using TMAH for example, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass in the total mass of the developer.

[0378] When the developer contains an organic solvent, the organic solvent is, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyl oxyacetates (e.g., methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionic acid (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkyloxypropionic acid (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-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, etc., and, as ethers, for example, diethylene 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably exemplified.

[0379] When the developer contains an organic solvent, the organic solvent can be used alone or in a mixture of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

[0380] When the developer contains an organic solvent, the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Also, the above content may be 100% by mass.

[0381] The developer may further contain other components. Examples of other components include known surfactants and known antifoaming agents.

[0382] 〔Supply method of developer〕 The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and examples include a method of immersing a substrate on which a film is formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, and the like. From the viewpoints of the permeability of the developer, the removability of the non-image portion, and the manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of the permeability of the developer into the image portion, a method of supplying the developer with a spray nozzle is more preferable. Further, after continuously supplying the developer with a straight nozzle, the substrate may be spun to remove the developer from the substrate, and after spin drying, the substrate may be continuously supplied again with a straight nozzle and then the substrate may be spun to remove the developer from the substrate, and this process may be repeated a plurality of times. As the method of supplying the developer in the development step, a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer on the substrate is vibrated with ultrasonic waves or the like, and a combination of these steps can be adopted.

[0383] The development time is preferably from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes. The temperature of the developer during development is not particularly defined, but is preferably from 10 to 45°C, more preferably from 18°C to 30°C.

[0384] In the development step, after the treatment with the developer, further, the pattern may be washed (rinsed) with a rinse liquid. Also, a method such as supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.

[0385] 〔Rinse Liquid〕 When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0386] When the rinse liquid contains an organic solvent, examples of the organic solvent as esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkyl alkoxyacetate, ethyl alkyl alkoxyacetate, butyl alkyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-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, etc., and as ethers, for example, diethylene 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably exemplified.

[0387] When the rinse liquid contains an organic solvent, the organic solvent can be used singly or in a mixture of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are even more preferable.

[0388] When the rinse liquid contains an organic solvent, it is preferable that 50 mass% or more of the rinse liquid is an organic solvent, more preferably 70 mass% or more is an organic solvent, and even more preferably 90 mass% or more is an organic solvent. Also, the rinse liquid may be 100 mass% organic solvent.

[0389] The rinse liquid may further contain other components. Examples of other components include known surfactants and known antifoaming agents.

[0390] 〔Method for supplying the rinse liquid〕 The method for supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and examples include a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid in a liquid pool on the substrate, a method of supplying the rinsing liquid to the substrate by showering, and a method of continuously supplying the rinsing liquid to the substrate by means such as a straight nozzle. From the viewpoints of the penetrability of the rinsing liquid, the removability of the non-image portion, and the manufacturing efficiency, there is a method of supplying the rinsing liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying with a spray nozzle is preferable. From the viewpoint of the penetrability of the rinsing liquid into the image portion, a method of supplying with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, it is preferable that the rinsing step is a step of supplying the rinsing liquid to the film after the exposure with a straight nozzle or continuously supplying it, and it is more preferable that the rinsing liquid is supplied with a spray nozzle. In addition, as the method for supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept in a substantially stationary state on the substrate, a step in which the rinsing liquid on the substrate is vibrated with ultrasonic waves or the like, and a step combining them can be adopted.

[0391] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly defined, but preferably, it can be carried out at 10 to 45°C, and more preferably at 18°C to 30°C.

[0392] <Heating step> The pattern obtained by the developing step (when the rinsing step is performed, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above development. That is, the method for producing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. In addition, the method for producing the cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step, or a film obtained by the film forming step. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimides. Also, crosslinking of unreacted crosslinkable groups in the specific resin or crosslinking agents other than the specific resin also proceeds. As the heating temperature (maximum heating temperature) in the heating step, 50 to 450 °C is preferable, 150 to 350 °C is more preferable, 150 to 250 °C is still more preferable, 160 to 250 °C is even more preferable, and 160 to 230 °C is particularly preferable.

[0393] The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generator, bases generated from the compound B, etc. by heating.

[0394] In the heating step, the heating is preferably performed at a temperature rising rate of 1 to 12 °C / min from the starting temperature of heating to the maximum heating temperature. The above temperature rising rate is more preferably 2 to 10 °C / min, and still more preferably 3 to 10 °C / min. By setting the temperature rising rate to 1 °C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rising rate to 12 °C / min or less, it is possible to relieve the residual stress of the cured product. In addition, in the case of an oven capable of rapid heating, it is preferably performed at a temperature rising rate of 1 to 8 °C / sec from the starting temperature of heating to the maximum heating temperature, more preferably 2 to 7 °C / sec, and still more preferably 3 to 6 °C / sec.

[0395] The starting temperature of heating is preferably 20 °C to 150 °C, more preferably 20 °C to 130 °C, and still more preferably 25 °C to 120 °C. The starting temperature of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied onto a substrate and then dried, it is the temperature of the film (layer) after this drying, and for example, it is preferable to raise the temperature from a temperature 30 to 200 °C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0396] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0397] Particularly when forming a multi-layer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0398] Heating may be performed stepwise. As an example, steps such as heating from 25°C to 120°C at 3°C / min, holding at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C / min, and holding at 180°C for 120 minutes may be performed. Also, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment while irradiating ultraviolet rays. It is possible to improve the characteristics of the film by such a pretreatment process. The pretreatment process is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may also be in two or more steps. For example, the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. Furthermore, it may be cooled after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0399] The heating step is preferably performed in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or performing it under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, and examples include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven, etc.

[0400] <Post-development exposure process> The (pattern after rinsing when a rinsing step is performed), obtained by the developing step, may be subjected to a post-development exposure step of exposing the pattern after the developing step, instead of, or in addition to, the above heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions that promote the cyclization of a polyimide precursor or the like by the photosensitization of a photo-base generator, reactions that promote the elimination of an acid-decomposable group by the photosensitization of a photo-acid generator, and the like can be promoted. In the post-development exposure step, at least a part of the pattern obtained in the developing step may be exposed, but it is preferable that the entire pattern is exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength at which the photosensitive compound has sensitivity. 2 It is more preferably 100 to 15,000 mJ / cm. 2 It is even more preferable. The post-development exposure step can be performed, for example, using the light source in the above-described exposure step, and it is preferable to use broadband light.

[0401] <Metal layer formation step> The pattern obtained by the developing step (preferably the one subjected to at least one of the heating step and the post-exposure developing step) may be subjected to a metal layer formation step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation step of forming a metal layer on the pattern (preferably the one subjected to at least one of the heating step and the post-development exposure step) obtained by the developing step.

[0402] As the metal layer, existing metal species can be used without particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferable, and copper is even more preferable.

[0403] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using a copper sulfate or copper cyanide plating solution.

[0404] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0405] <Use> Examples of the method for producing the cured product of the present invention or the fields applicable to the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, there are sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuits), or patterning the insulating films for mounting applications as described above by etching. For these applications, reference can be made to, for example, "High Functionality and Application Technology of Polyimide" by Science & Technology Co., Ltd., April 2008, supervised by Masaki Kakinoto, "Fundamentals and Development of Polyimide Materials" published by CMC Technical Library, November 2011, "Latest Polyimide: Fundamentals and Applications" edited by the Japan Polyimide and Aromatic Polymer Research Society, NTS, August 2010, and the like.

[0406] Further, the method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of plate surfaces such as offset plate surfaces or screen plate surfaces, the use of molded parts for etching, electronics, particularly in the production of protective lacquers and dielectric layers in microelectronics.

[0407] (Laminate, and method for producing laminate) The laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention. The laminate of the present invention is a laminate including two or more layers made of the cured product, and may be a laminate laminated with three or more layers. Among the two or more layers made of the cured product included in the above laminate, at least one layer is made of the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0408] That is, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention a plurality of times.

[0409] The laminate of the present invention preferably includes two or more layers made of a cured product and includes a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product during the method for manufacturing the cured product that is performed multiple times. The preferred embodiment of the metal layer forming step is as described above. As the laminate, for example, a laminate preferably including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order can be mentioned. Both the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product may be compositions having the same composition or compositions having different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

[0410] <Lamination step> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film forming step (layer forming step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step, in this order, again on the surface of a pattern (resin layer) or a metal layer. However, an embodiment in which at least one of the film forming step of (a) and the heating step and the post-development exposure step of (d) is repeated may be employed. Further, a metal layer forming step (e) may be included after at least one of the heating step and the post-development exposure step of (d). Needless to say, the drying step and the like may be appropriately included in the lamination step.

[0411] After the lamination process, when performing the lamination process again, after the exposure process, after the heating process, or after the metal layer formation process, a surface activation treatment process may be further performed. Examples of the surface activation treatment include plasma treatment. Details of the surface activation treatment will be described later.

[0412] The lamination process is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a configuration in which there are 2 or more and 20 or less resin layers, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration in which there are 2 or more and 9 or less resin layers is more preferable. Each of the above layers may have the same or different composition, shape, film thickness, etc.

[0413] In the present invention, in particular, after providing the metal layer, a mode of forming a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer is preferable. Specifically, a mode of repeating in the order of (a) film formation process, (b) exposure process, (c) development process, (d) heating process and at least one of post-development exposure process (e) metal layer formation process, or (a) film formation process, (d) heating process and at least one of post-development exposure process, (e) metal layer formation process. By alternately performing the lamination process of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation process, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0414] (Surface activation treatment process) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment process for surface-activating at least a part of the metal layer and the resin composition layer. The surface activation treatment process is usually performed after the metal layer formation process, but after the development process, the surface activation treatment process may be performed on the resin composition layer and then the metal layer formation process may be performed. The surface activation treatment may be performed only on at least a part of the metal layer, or only on at least a part of the resin composition layer after exposure, or may be performed on at least a part of both the metal layer and the resin composition layer after exposure, respectively. It is preferable to perform the surface activation treatment on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer where the resin composition layer is formed on the surface. Thus, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on the surface can be improved. In addition, it is preferable to perform the surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. Thus, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or resin layer provided on the surface that has been surface-activated can be improved. Particularly when negative development is performed, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved. Specific examples of the surface activation treatment include plasma treatment of various source gases (such as oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas), corona discharge treatment, etching treatment with CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, surface treatment by ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing at least one of an amino group and a thiol group after immersing in an aqueous hydrochloric acid solution to remove the oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferable, and particularly oxygen plasma treatment using oxygen as the source gas is preferable. In the case of corona discharge treatment, the energy is preferably 500~200,000 J / m 2 is preferable, 1000~100,000 J / m 2 is more preferable, and 10,000~50,000 J / m 2 is most preferable.

[0415] (Method for manufacturing a semiconductor device) In addition, the present invention also discloses a semiconductor device including the cured product of the present invention or the laminate of the present invention. The present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 can be referred to, and these contents are incorporated herein.

Examples

[0416] The present invention will be described more specifically with reference to the following exa...

Claims

1. At least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and a compound B that generates a base by the action of a base, wherein the compound B is a compound represented by the following formula (1-2) or formula (1-3), a resin composition; 【Chemical 1】 In formula (1-2), R １ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ２ represents an optionally substituted hydrocarbon group. R １ and R ２ may combine to form a ring structure. R ３ each independently represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ４ represents a cyano group, a nitro group, -C(=O)OR, -OC(=O)R, a fluorinated alkyl group, or a halogen atom, and R represents an optionally substituted hydrocarbon group; In formula (1-3), R １ represents a hydrogen atom or an optionally substituted hydrocarbon group, R ２ represents an optionally substituted hydrocarbon group, R １ and R ２ may combine to form a ring structure, R ３ each independently represents a hydrogen atom or an optionally substituted hydrocarbon group, and Ar represents an aromatic group substituted with at least one group selected from a cyano group, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) ２ R, a perfluoroalkyl group, and a halogen atom, and R represents an optionally substituted hydrocarbon group.

2. The resin composition according to claim 1, wherein the base generated from the compound B is an amine.

3. The resin composition according to claim 1 or 2, wherein the compound B has a urethane bond.

4. The resin composition according to any one of claims 1 to 3, further comprising a solvent.

5. The resin composition according to any one of claims 1 to 4, further comprising a thermal base generator or a photo base generator.

6. The resin composition according to any one of claims 1 to 5, further comprising a thermal base generator.

7. The resin composition according to any one of claims 1 to 6, further comprising a photoinitiator.

8. The resin composition according to any one of claims 1 to 7, further comprising a sensitizer.

9. The resin composition according to any one of claims 1 to 8, further comprising a polymerizable compound.

10. A cured product obtained by curing the resin composition according to any one of claims 1 to 9.

11. A laminate comprising two or more layers of the layer made of the cured product according to claim 10 and including a metal layer between any of the layers made of the cured product.

12. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 9 onto a substrate to form a film.

13. The method for producing a cured product according to claim 12, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

14. The method for producing a cured product according to claim 12 or 13, comprising a heating step of heating the film at 50 to 450 °C.

15. A semiconductor device comprising the cured product according to claim 10 or the laminate according to claim 11.

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